Multimodal ethylene-based polymer processing systems and methods

ABSTRACT

Embodiments of methods for producing a trimodal polymer in a solution polymerization process comprise three solution polymerization reactors organized in parallel or in series.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a National Stage Entry under 35 U.S.C. § 371 ofInternational Patent Application No. PCT/US2018/066462, filed Dec. 19,2018, which claims priority to U.S. Provisional Application Ser. No.62/610,383, filed Dec. 26, 2017, both of which are hereby incorporatedby reference in their entireties.

TECHNICAL FIELD

Embodiments of the present disclosure generally relate to systems andmethods for multimodal ethylene-based polymer processing. Morespecifically, embodiments of the present disclosure relate to reactorconfigurations and methods of using these configurations to producepolymers, in particular, multimodal ethylene-based polymers (e.g.,trimodal polymers).

BACKGROUND

Polyethylene is one of the most common plastics and may be used in avariety ways depending on the structure of the polymer, for example,bags/liners, caps/closures, hygiene films, industrial injection molding,etc. It has been estimated that approximately 80 million tons ofpolyethylene is produced each year. In order to meet demand as well asprovide new polymer structures with useful properties, it is necessaryto provide new polymer processing systems and methods.

Particularly useful polyethylene structures are multimodalethylene-based polymers, e.g., trimodal polymers, because they maycombine the processability of resin with a balance of desirableproperties such as strength, barrier properties, etc. However, theproduction of multimodal ethylene-based polymers is still challengingand problematic as gelling, especially for the high molecular weightcomponent, process control, and other issues may arise. Accordingly,there is a continual need for improved processes for making multimodalethylene-based polymers.

SUMMARY

Embodiments of the present disclosure address the needs discussed aboveby including a system having three solution polymerization reactors, oneof which is an adiabatic reactor. The adiabatic reactor may produce ahigh molecular weight component for the multimodal ethylene-basedpolymer, while ensuring the viscosity is maintained at a manageablelevel such that gelling is prevented.

According to one embodiment, a method of producing a trimodal polymer ina solution polymerization process is provided. The method comprisesintroducing at least one catalyst, ethylene monomer, at least one C₃-C₁₂α-olefin comonomer, solvent, and optionally hydrogen to a first solutionpolymerization reactor to produce an effluent comprising a firstethylene-based component, wherein the first ethylene-based component hasa density (ρ₁) as measured according to ASTM D792, and a weight-averagemolecular weight (M_(w(GPC),1)) as measured according to Gel PermeationChromatography (GPC). Additionally, the method comprises introducing atleast one catalyst, ethylene monomer, at least one C₃-C₁₂ α-olefincomonomer, solvent, and optionally hydrogen to a second solutionpolymerization reactor downstream from the first solution polymerizationreactor to produce an effluent comprising the first ethylene-basedcomponent and a second ethylene-based component, wherein the secondethylene-based component has a density (ρ₂), and a weight-averagemolecular weight (M_(w(GPC),2)) Further, the method comprisesintroducing the first ethylene-based component, the secondethylene-based component, at least one catalyst, ethylene monomer, atleast one C₃-C₁₂ α-olefin comonomer, solvent, and optionally hydrogen toa third solution polymerization reactor downstream from the secondsolution polymerization reactor to produce an effluent comprising thetrimodal polymer, wherein the trimodal polymer comprises the firstethylene-based component, the second ethylene-based component, and athird ethylene-based component, wherein the third ethylene-basedcomponent has a density (ρ₃), and a weight-average molecular weight(M_(w(GPC),3)). Moreover, the first solution polymerization reactor orthe third polymerization reactor is an adiabatic reactor, and each ofρ₁, ρ₂, and ρ₃ have different densities and each of M_(w(GPC),1),M_(w(GPC),2), and M_(w(GPC),3) have different weight-average molecularweights.

According to yet another method of producing a trimodal polymer in asolution polymerization process, the method comprises introducing atleast one catalyst, ethylene monomer, at least one C₃-C₁₂ α-olefincomonomer, solvent, and optionally hydrogen to a first solutionpolymerization reactor to produce an effluent comprising a firstethylene-based component, wherein the first ethylene-based component hasa density (ρ₁) as measured according to ASTM D792, and a weight-averagemolecular weight (M_(w(GPC),1)) as measured according to Gel PermeationChromatography (GPC). Further, the method comprises introducing at leastone catalyst, ethylene monomer, at least one C₃-C₁₂ α-olefin comonomer,solvent, and optionally hydrogen in the second solution polymerizationreactor to produce an effluent comprising a second ethylene-basedcomponent, wherein the second ethylene-based component has a density(ρ₂), and a weight-average molecular weight (M_(w(GPC),2)) Additionally,the method comprises introducing at least one catalyst, ethylenemonomer, at least one C₃-C₁₂ α-olefin comonomer, solvent, and optionallyhydrogen to the third solution polymerization reactor to produce aneffluent comprising a third ethylene-based component, wherein the thirdethylene-based component has a density (ρ₃), and a weight-averagemolecular weight (M_(w(GPC),3)) Further, the method comprises mixing thefirst ethylene-based component, the second ethylene-based component, andthe third ethylene-based component to produce the trimodal polymer.Moreover, the first solution polymerization reactor or the thirdpolymerization reactor is an adiabatic reactor, and each of ρ₁, ρ₂, andρ₃ have different densities and each of M_(w(GPC),1), M_(w(GPC),2), andM_(w(GPC),3) have different weight-average molecular weights.

BRIEF DESCRIPTION OF THE DRAWINGS

The following detailed description of specific embodiments of thepresent disclosure can be best understood when read in conjunction withthe drawings enclosed herewith.

FIG. 1 is a schematic depiction of a series reactor system configurationin accordance with one or more embodiments of the present disclosure.

FIG. 2 is a schematic depiction of a parallel reactor systemconfiguration in accordance with one or more embodiments of the presentdisclosure.

FIG. 3 is a graphical illustration of a Crystallization ElutionFractionation (CEF) overlay.

For the purpose of describing the simplified schematic illustrations anddescriptions of FIGS. 1 and 2 , the numerous valves, heat exchangers,agitators, temperature sensors, electronic controllers and the like thatmay be employed and are well known to those of ordinary skill in the artof certain chemical processing operations are not included. It should beunderstood that these components are within the spirit and scope of thepresent embodiments disclosed.

It should be understood that two or more process streams are “mixed”,“combined” or “split” when two or more lines intersect or meet at ajunction in the schematic flow diagrams of FIGS. 1 and 2 . Mixing orcombining may also include mixing by directly introducing both streamsinto a like reactor, separation device, or other system component. Forexample, it should be understood that when two streams are depicted asbeing combined directly prior to entering a reactor, that in someembodiments the streams could equivalently be introduced into thereactor and be mixed in the reactor.

DETAILED DESCRIPTION Definitions

The term “polymer” refers to a polymeric compound prepared bypolymerizing monomers, whether of the same or a different type. Thegeneric term polymer thus embraces the term “homopolymer,” usuallyemployed to refer to polymers prepared from only one type of monomer aswell as “copolymer,” which refers to polymers prepared from two or moredifferent monomers. The term “interpolymer,” as used herein, refers to apolymer prepared by the polymerization of at least two different typesof monomers. The generic term interpolymer thus includes copolymers, andpolymers prepared from more than two different types of monomers, suchas terpolymers.

“Polyethylene” or “ethylene-based polymer” shall mean polymerscomprising greater than 50% by weight of units which have been derivedfrom ethylene monomer. This includes polyethylene homopolymers orcopolymers (meaning units derived from two or more comonomers). Commonforms of polyethylene known in the art include Low Density Polyethylene(LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low DensityPolyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-sitecatalyzed Linear Low Density Polyethylene, including both linear andsubstantially linear low density resins (m-LLDPE); Medium DensityPolyethylene (MDPE); and High Density Polyethylene (HDPE).

As used herein, “multimodal” means compositions that can becharacterized by having at least three polymer subcomponents withvarying densities and weight-average molecular weights, and optionally,may also have different melt index values. In one embodiment, multimodalmay be defined by having at least three distinct peaks in a GelPermeation Chromatography (GPC) chromatogram showing the molecularweight distribution. In another embodiment, multimodal may be defined byhaving at least three distinct peaks in a Crystallization ElutionFractionation (CEF) chromatogram showing the short chain branchingdistribution. Multimodal includes resins having three peaks as well asresins having more than three peaks.

The term “trimodal polymer” means a multimodal ethylene-based polymerhaving three primary components: a first ethylene-based polymercomponent, a second ethylene-based polymer component, and a thirdethylene-based polymer component.

“Polyethylene component”, for example, the “first ethylene-basedcomponent”, the “second ethylene-based component”, or the “thirdethylene-based component” refer to subcomponents of the multimodal ortrimodal polymer, wherein each subcomponent is an ethylene interpolymercomprising ethylene monomer and C₃-C₁₂ α-olefin comonomer.

As used herein, the term “adiabatic reactor” refers to a solutionpolymerization reactor or vessel operating without the addition orremoval of heat. Consequently, the “adiabatic reactor” may be a reactornot coupled to or in communication with a heat exchanger.

As used herein, the “solution polymerization reactor” is a vessel, whichperforms solution polymerization, wherein ethylene monomer and at leastC₃-C₁₂ α-olefin comonomer copolymerize after being dissolved in anon-reactive solvent that contains a catalyst. In the solutionpolymerization process, hydrogen may be utilized; however, it is notrequired in all solution polymerization processes.

System Embodiments

In some embodiments, the disclosure provides for system having at leastthree reactors for producing multimodal ethylene-based polymers, whereinthe systems provide additional control in producing specific types ofpolymers, in particular, trimodal polymers.

An example of a reactor system utilizing three reactors in series isshown in FIG. 1 . As shown in FIG. 1 , the three reactors may comprise afirst solution polymerization reactor 101 followed sequentially by asecond solution polymerization reactor 102 and a third solutionpolymerization reactor 103. In one or more embodiments, the firstsolution polymerization reactor 101 or the third polymerization reactor103 is an adiabatic reactor. In a further embodiment, the first solutionpolymerization reactor 101 is an adiabatic reactor.

In certain methods, which utilize the three reactor configurationdisclosed in FIG. 1 , it is possible to produce, among other things, amultimodal ethylene-based polymer, specifically a trimodal polymer. Onemethod of producing a trimodal polymer in the reactor system 1 of FIG. 1involves introducing at least one catalyst, ethylene monomer, at leastone C₃-C₁₂ α-olefin comonomer, solvent, and optionally hydrogen in thefirst solution polymerization reactor 101 to produce an effluent 20comprising a first ethylene-based component. The feed to the reactor isdepicted as two streams 10 and 11, where stream 10 is the feed ofmonomer and C₃-C₁₂ α-olefin comonomer and stream 11 is the feed ofcatalyst/cocatalyst and solvent. However, it is contemplated that moreor less feed inlets may be used.

Referring again to FIG. 1 , the effluent 20 comprising the firstethylene-based component is then transferred to the second solutionpolymerization reactor 102 along with at least one catalyst, ethylenemonomer, at least one C₃-C₁₂ α-olefin comonomer, solvent, and optionallyhydrogen. The second solution polymerization reactor 102 reacts thematerials together to produce an effluent 30 comprising the firstethylene-based component, and a second ethylene-based component. Theeffluent 30 comprising the second ethylene-based component is thentransferred to the third solution polymerization reactor 103 along withat least one catalyst, ethylene monomer, at least one C₃-C₁₂ α-olefincomonomer, solvent, and optionally hydrogen.

The third solution polymerization reactor 103 then mixes the materialstogether to produce an effluent comprising the first and secondethylene-based components as well as the third ethylene-based component,wherein these three ethylene-based polymer components make up thetrimodal polymer.

When the reactor system shown in FIG. 1 is connected in series, thefirst solution polymerization reactor 101 may operate at the samepressure as the second solution polymerization reactor 102 and/or thethird solution polymerization reactor 103. In one embodiment, all threereactors 101, 102, 103 may operate at the same pressure. To this end,the reactors may be configured to minimize pressure drop between eachother.

As an alternative to the three reactor series embodiment depicted inFIG. 1 , it is possible for a parallel three reactor system as shown inFIG. 2 . As shown in FIG. 2 , a first solution polymerization reactor101 may receive a monomer feed 11, a catalyst, a solvent feed 10, andoptionally hydrogen. These inlets may be further separated or combineddepending on the system. In the first solution polymerization reactor101, the at least one catalyst, ethylene monomer, at least one C₃-C₁₂α-olefin comonomer, solvent, and optionally hydrogen react to produce aneffluent 20 comprising the first ethylene-based component. In theembodiment of FIG. 2 , the feed may be split into multiple streams forexample, 121, 122, and 123. In other embodiments, the effluent 20 is notsplit into multiple streams and thus substantially the entire effluentis fed to the second solution polymerization reactor 102, and/or thethird polymerization reactor 103, which operates in parallel to thesecond solution polymerization reactor 102.

Referring again to an embodiment depicted in FIG. 2 , the effluent 121comprising the first ethylene-based component is passed to the secondsolution polymerization reactor 102, wherein the first ethylene-basedcomponent is mixed with at least one catalyst, ethylene monomer, atleast one C₃-C₁₂ α-olefin comonomer, solvent, and optionally hydrogen toproduce an effluent 130 comprising the first ethylene-based componentand a second ethylene-based component. While not shown in FIGS. 1 and 2, the feed components (catalyst, ethylene monomer, at least one C₃-C₁₂α-olefin comonomer) may be fed separately from the feeds of the secondsolution polymerization reactor 102 and the third solutionpolymerization reactor 103.

Referring again to FIG. 2 , the effluent 122, which comprises the firstethylene-based component, may also be passed to the third solutionpolymerization reactor 103. Within the third solution polymerizationreactor 103, the first ethylene-based component, the catalyst, ethylenemonomer, the C₃-C₁₂ α-olefin comonomer, the solvent, and optionally thehydrogen react to produce an effluent 135 comprising the firstethylene-based component and a third ethylene-based component. Theeffluents produced by the second polymerization reactor 102 and thethird polymerization reactor 103 are then mixed together to produce atrimodal polymer 40. This is depicted at junction 112; however, othermixing locations and are contemplated. Additionally, in a furtherembodiment, at least a portion 132 of the effluent 130 from the firstpolymerization reactor 102 may be passed to the second polymerizationreactor 103. In specific embodiment, the effluent stream may be split atjunction 114, which may represent a flow splitter.

Various temperature conditions are contemplated for three solutionpolymerization reactors. For example, the temperatures of the reactorsmay be in the range from 115 to 215° C. The reactor temperatures foreach may be varied based on the final trimodal polymer sought.

In some embodiments, the systems of FIGS. 1 and 2 may comprise a tubularreactor 104, which allows for further reaction and conversion of thetrimodal polymer 104. In general, the tubular reactor 104 providesadditional conversion of the components of the trimodal polymer byincreasing the residence time. Moreover, the tubular reactor 104 mayimprove catalyst efficiency by allowing the reactors to run at higherethylene concentrations and reducing energy consumption by raising thepolymer temperature and thereby reducing the heat input required beforea solvent removal step. Various reactors are considered suitable andwould be familiar to one of ordinary skill in the art.

Additional process steps can be included in the systems of FIGS. 1 and 2, for example, catalyst kill steps. Catalyst kill steps may involve theaddition of a polar compound to deactivate the polymerization catalysts.Suitable polar compounds used as catalyst kill agents may include water,polyethylene glycol, butylated hydroxytoluene (BHT), glycerol, orcombinations thereof

Other process flows and alterations, as would be recognized by a personof ordinary skill in the art, are within the scope of FIGS. 1 and 2 .

Trimodal Polymer

As stated above, the yield of the systems depicted in FIGS. 1 and 2 is atrimodal polymer, which as stated above is an example of a multi-modalethylene-based polymer. In certain embodiments of the trimodal polymer,the first ethylene-based component, the second ethylene-based component,and the third ethylene-based component may be defined by density (ρ₁,ρ₂, and ρ₃, respectively), weight average molecular weight(M_(w(GPC),1), M_(w(GPC),2), and M_(w(GPC),3), respectively), and/ormelt index (MI₁, MI₂, and MI₃, respectively).

For the trimodal polymer, the densities (ρ₁, ρ₂, and ρ₃) for the firstethylene-based component, the second ethylene-based component, and thethird ethylene-based component, respectively, may each have differentdensity values. Similarly, the weight-average molecular weights(M_(w(GPC),1), M_(w(GPC),2), and M_(w(GPC),3)) may each have differentweight-average molecular weight values. Without being bound by theory,the variance in densities and molecular weights between the firstethylene-based component, the second ethylene-based component, and thethird ethylene-based component enables the trimodal polymer to have adesired combination of strength and processibility.

In further embodiments, the trimodal polymer may be defined such that ρ₁is less than ρ₂ and is also less than ρ₃ and wherein M_(w(GPC),1) isgreater than M_(w(GPC),2) and is also greater than M_(w(GPC),3). Infurther embodiments, MI₁ is less than MI₂ and MI₁ is also less than MI₃.In one embodiment, the final product may be defined such that ρ₁<ρ₂<ρ₃,and M_(w(GPC),3)>M_(w(GPC),2)>M_(w(GPC),1). In such an embodiment, thefirst ethylene-based component may be considered as the low densitycomponent, the second ethylene-based component may be considered as theintermediate density component, the third ethylene-based component maybe considered the high density component. In order to achieve suchdistributions, the catalyst in the first solution polymerization reactormay differ from the catalyst used in the second solution polymerizationreactor and the catalyst used in the third solution polymerizationreactor. In other embodiments, the distribution may be achieved by usinga different catalyst in each of the first solution polymerizationreactor, the second solution polymerization reactor, and the thirdsolution polymerization reactor. In yet another embodiment, the meltindex of the trimodal polymer may be defined as follows: MI₁<MI₂<MI₃.

In one or more embodiments, densities of the first ethylene-basedcomponent (ρ₁), the second ethylene-based component (ρ₂), and the thirdethylene-based component (ρ₃) may be 0.855 g/cc to 0.935 g/cc, 0.885 to0.945 g/cc, and 0.900 to 0.980 g/cc, respectively. In furtherembodiments, the first ethylene-based component may have a density (ρ₁)from 0.865 g/cc to 0.920 g/cc, or from 0.870 to 0.910 g/cc. Moreover,the second ethylene-based component may have a density (ρ₂) from 0.890g/cc to 0.930 g/cc, or from 0.895 g/cc to 0.925 g/cc. Further, the thirdethylene-based component may have a density (ρ₃) from 0.920 g/cc to0.980 g/cc, or from 0.935 g/cc to 0.9670 g/cc. In some embodiments, thefinal density of the trimodal polymer may be from 0.900 g/cc to 0.960g/cc, or from 0.905 g/cc to 0.950 g/cc, or from 0.910 g/cc to 0.940g/cc.

In one or more embodiments, the weight average molecular weights of thefirst ethylene-based component (M_(w(GPC),1)), the second ethylene-basedcomponent (M_(w(GPC),2)), and the third ethylene-based component(M_(w(GPC),3)) are 90 kg/mol to 500 kg/mol, 70 kg/mol to 300 kg/mol, and10 kg/mol to 170 kg/mol, respectively. In further embodiments, the firstethylene-based component may have a weight average molecular weight(M_(w(GPC),1)) of 100 kg/mol to 363 kg/mol, or from 150 kg/mol to 350kg/mol. Moreover, in further embodiments, the second ethylene-basedcomponent may have a weight average molecular weight (M_(w(GPC),2)) of100 kg/mol to 200 kg/mol, or from 110 kg/mol to 190 kg/mol, or from 120kg/mol to 175 kg/mol, or from 120 kg/mol to 170 kg/mol. Furthermore, inadditional embodiments, the third ethylene-based component may have aweight average molecular weight (M_(w(GPC),3)) of 15 kg/mol to 160kg/mol, or from 16 kg/mol to 120 kg/mol, or from 17 kg/mol to 90 kg/mol,or from 18 kg/mol to 60 kg/mol.

Similarly, in some embodiments, the first ethylene-based component has amelt index (MI_(i)) of from 0.001 g/10 min to 1.0 g/10 min, or from 0.01g/10 min to 0.5 g/10 min, or from 0.01 g/10 min to 0.1 g/10 min.Moreover, the second ethylene-based component may have a melt index(MI₂) of from 0.01 g/10 min to 2.0 g/10 min, or from 0.1 g/10 min to 1.0g/10 min, or from 0.2 g/10 min to 0.7 g/10 min. Further, the thirdethylene-based component may have a melt index (MI₃) of from 0.1 g/10min to 5000 g/10 min, or from 0.5 g/10 min to 4000 g/10 min, or from 1g/10 min to 3000 g/10 min, or from 10 g/10 min to 1000 g/10 min, or from50 g/10 min to 750 g/10 min. In further embodiments, the trimodalpolymer has a melt index (I₂) of from 0.1 g/10 min to 10.0 g/10 min, orfrom 0.2 to 5.0 g/10 min, or from 0.5 to 1.0 g/10 min.

Various amounts are contemplated for the components of the trimodalpolymer. In one or more embodiments, the trimodal polymer may comprisefrom 2 to 45% by weight of the first ethylene-based component, or from20 to 45% by weight of the first ethylene-based component, or from orfrom 25 to 45% by weight of the first ethylene-based component.Moreover, the trimodal polymer may comprise from 2 to 40% by weight ofthe second ethylene-based component, or from 5 to 40% by weight of thesecond ethylene-based component, or from or from 10 to 35% by weight ofthe second ethylene-based component. Moreover, the trimodal polymer maycomprise from 30 to 70% by weight of the third ethylene-based component,or from 35 to 65% by weight of the third ethylene-based component, orfrom 40 to 60% by weight of the third ethylene-based component, or from45 to 55% by weight of the third ethylene-based component.

Reactors

Various embodiments are contemplated for the first, second and thirdsolution polymerization reactors. As stated above, at least one of thefirst, second, and third solution polymerization reactors is anadiabatic reactor. In specific embodiments, the first solutionpolymerization reactor is an adiabatic reactor.

Various vessels are contemplated for use as the adiabatic reactor. Inone or more embodiments, the adiabatic reactor may comprise a staticmixer, a mechanical mixer, or a continuous stirred tank reactor (CSTR).In a specific embodiment, the first solution polymerization reactor 101may be a continuous stirred tank reactor (CSTR). While various reactorsizes are contemplated, in some embodiments, the first solutionpolymerization reactor 101 may be half or less than half of the volumeof the second solution polymerization reactor 102 and/or the thirdsolution polymerization reactor 103. While the first solutionpolymerization reactor 101 is discussed herein for producing the firstethylene-based component, it is contemplated that the first solutionpolymerization reactor 101 could be used for the other polyethylenecomponents.

These may include conventional reactors such as loop reactors, sphericalreactors, isothermal reactors, stirred tank reactors, batch reactors, orany combinations thereof. In one embodiment, the second solutionpolymerization reactor 102, the third solution polymerization reactor103, or both may include loop reactors. Moreover, the second solutionpolymerization reactor 102, the third solution polymerization reactor103, or both may each include single reactor vessels, or multiplereactors in series or parallel. In one or more embodiments, a two loopvessels or three loop vessels may be used for the second solutionpolymerization loop reactor 102, the third solution polymerization loopreactor 103, or both.

In a specific embodiment, the first solution polymerization reactor 101is an adiabatic continuous stirred tank reactor, while the secondsolution polymerization reactor 102 and the third solutionpolymerization reactor 103 are loop reactors.

In further embodiments, the first and second solution polymerizationloop reactors may comprise one or more pumps (not shown). A pump maytransport at least a portion of a reaction stream at least a portion ofthe way around a flow loop. For example, a pump may transport at least aportion of a reaction stream from a heat exchanger to a product outlet.

Moreover, each loop reactor may comprise one or more heat exchangers(not shown) and, optionally, pipes connecting them to each other and/orto the remainder of the reactor, according to some embodiments. A flowloop may be configured, in some embodiments, with or withoutinterconnecting pipes between components. In some embodiments, it may bedesirable to configure every element along the flow path to act as areaction zone. In such embodiments, the regions where heat transfertakes place may be maximized at the expense of connecting pipes wherethe transfer is minimal or non-existent. A heat exchanger may comprise,in some embodiments, at least one cooling fluid inlet and at least onecooling fluid outlet. According to some embodiments, a heat exchangermay further comprise at least one reaction stream inlet and at least onereaction stream outlet. In some embodiments, any heat exchange apparatusmay be used, in any configuration. For example, a heat exchanger mayinclude a cooling coil positioned in a flow loop. In another example, aheat exchanger may include a shell-and-tube heat exchanger positioned ina flow loop wherein the flow stream passes through the tubes. In anotherexample, an entire flow loop may be configured as a heat exchanger byenclosing it in a cooling jacket or double piping.

Feed Components

Various embodiments are contemplated for the C₃-C₁₂ comonomer, solvent,and catalysts.

In some embodiments, the C₃-C₁₂ α-olefin comonomer is propene, butene,pentene, hexene, pentene, octene, nonene, decene, undecene, dodecene, orcombinations thereof. In specific embodiments, the C₃-C₁₂ α-olefincomonomer is octene. It is contemplated that the same C₃-C₁₂ α-olefincomonomer is used in all three reactors. Alternatively, it iscontemplated that the C₃-C₁₂ α-comonomer may differ in the three reactorsystems depicted in FIGS. 1 and 2 .

Various solvents are considered suitable for use in the adiabaticreactor, and the first and second solution polymerization reactors. Thesolvents may vary based on the catalyst used in the specific reactors.Solvents may include, for example, paraffinic/isoparaffinic solvents,olefinic solvents, aromatic solvents, cyclic solvents, and combinationsthereof. Exemplary solvents include, but are not limited to,isoparaffins. For example, such isoparaffin solvents are commerciallyavailable under the name ISOPAR E from ExxonMobil Chemical.

Catalysts

As stated above, the catalysts may vary between adiabatic reactors andsolution polymerization reactors in order to impart different propertiesto the first ethylene-based component, the second ethylene-basedcomponent and third ethylene-based component.

Various catalysts are considered suitable. These may include, but arenot limited to, a Ziegler-Natta catalyst, a chromium catalyst, ametallocene catalyst, a post-metallocene catalyst, a constrainedgeometry complex (CGC) catalyst, a phosphinimine catalyst, or abis(biphenylphenoxy) catalyst. Details and examples of CGC catalysts areprovided in U.S. Pat. Nos. 5,272,236; 5,278,272; 6,812,289; and WOPublication 93/08221, which are all incorporated herein by reference intheir entirety. Details and examples of bis(biphenylphenoxy) catalystsare provided in U.S. Pat. Nos. 6,869,904; 7,030,256; 8,101,696;8,058,373; 9,029,487, which are all incorporated herein by reference intheir entirety. The catalysts utilized in the solution polymerizationreactors may vary in order to impart different properties to the firstethylene-based component, the second ethylene-based component, and thethird ethylene-based component. For example, it is contemplated to usedifferent catalysts in the first, second and third solutionpolymerization reactors to vary the density, melt index, comonomerincorporation, etc. of the first, second, and third ethylene-basedcomponents. Without being bound by theory, varying these parameters forthe first, second, and third ethylene-based components may enable themultimodal ethylene-based polymer to have a desired combination oftoughness and processability.

In one or more embodiments, the first solution polymerization reactor,the second solution polymerization reactor, and/or the third solutionpolymerization reactor may include homogenous or heterogeneouscatalysts. Homogeneous, often referred to as single-site, catalysts areorganometallic compounds which typically have a discrete molecularstructure, and are used to generate polymers, which have narrowmolecular weight distribution, as well as narrow compositiondistribution, in the case where interpolymers are made. Homogeneouscatalysts may be dissolved in a solution process or supported for use inparticle forming processes, such as slurry or gas phase. Heterogeneouscatalysts are not discrete compounds but rather result from a reactionmixture of metal compounds with precursors to form a complex, which hasmultiple active sites on some form of a particle. Polymers produced viaheterogeneous catalysts typically demonstrate broader molecular weightdistributions and, in the case of interpolymers, broader compositiondistributions than homogeneous catalysts.

The bis(biphenylphenoxy) catalyst is an example of a homogeneouscatalyst. Other examples of homogeneous catalysts include constrainedgeometry catalysts. Examples of heterogeneous catalysts may includeZiegler-Natta catalysts, which are particularly useful at the highpolymerization temperatures of the solution process. Examples of suchZiegler-Natta catalysts are those derived from organomagnesiumcompounds, alkyl halides or aluminum halides or hydrogen chloride, and atransition metal compound. Examples of such catalysts are described inU.S. Pat. No. 4,314,912 (Lowery, Jr. et al.), U.S. Pat. No. 4,547,475(Glass et al.), and U.S. Pat. No. 4,612,300 (Coleman, III), theteachings of which are incorporated herein by reference.

Particularly suitable organomagnesium compounds include, for example,hydrocarbon soluble dihydrocarbylmagnesium such as the magnesiumdialkyls and the magnesium diaryls. Exemplary suitable magnesiumdialkyls include particularly n-butyl-secbutylmagnesium,diisopropylmagnesium, di-n-hexylmagnesium, isopropyl-n-butyl-magnesium,ethyl-n-hexylmagnesium, ethyl-n-butylmagnesium, di-n-octylmagnesium andothers wherein the alkyl has from 1 to 20 carbon atoms. Exemplarysuitable magnesium diaryls include diphenylmagnesium, dibenzylmagnesiumand ditolylmagnesium. Suitable organomagnesium compounds include alkyland aryl magnesium alkoxides and aryloxides and aryl and alkyl magnesiumhalides with the halogen-free organomagnesium compounds being moredesirable.

Bis(biphenylphenoxy) catalysts are multi-component catalyst systemscomprising a bis(biphenylphenoxy) procatalyst, cocatalyst, as well asfurther optional ingredients. The bis(biphenylphenoxy) procatalyst mayinclude a metal-ligand complex according to Formula (I):

In Formula (I), M is a metal chosen from titanium, zirconium, orhafnium, the metal being in a formal oxidation state of +2, +3, or +4; nis 0, 1, or 2; when n is 1, X is a monodentate ligand or a bidentateligand; when n is 2, each X is a monodentate ligand and is the same ordifferent; the metal-ligand complex is overall charge-neutral; O is O(an oxygen atom); each Z is independently chosen from —O—, —S—,—N(R^(N))—, or P(R^(P))—; L is (C₁-C₄₀)hydrocarbylene or(C₁-C₄₀)heterohydrocarbylene, wherein the (C₁-C₄₀)hydrocarbylene has aportion that comprises a 1-carbon atom to 10-carbon atom linker backbonelinking the two Z groups in Formula (I) (to which L is bonded) or the(C₁-C₄₀)heterohydrocarbylene has a portion that comprises a 1-atom to10-atom linker backbone linking the two Z groups in Formula (I), whereineach of the 1 to 10 atoms of the 1-atom to 10-atom linker backbone ofthe (C₁-C₄₀)heterohydrocarbylene independently is a carbon atom orheteroatom, wherein each heteroatom independently is O, S, S(O), S(O)₂,Si(R^(C))₂, Ge(R^(C))₂, P(R^(C)), or N(R^(C)), wherein independentlyeach R^(C) is (C₁-C₃₀)hydrocarbyl or (C₁-C₃₀)heterohydrocarbyl; R¹ andR⁸ are independently selected from the group consisting of(C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃,—Ge(R^(C))₃, —P(R^(P))₂, —N(R^(N))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃,R^(C)S(O)—, R^(C)S(O)₂—, (R^(C))₂C═N—, R^(C)C(O)O—, R^(C)OC(O)—,R^(C)C(O)N(R^(N))—, (R^(N))₂NC(O)—, halogen, and radicals having Formula(II), Formula (III), or Formula (IV):

In Formulas (II), (III), and (IV), each of R³¹⁻³⁵, R⁴¹⁻⁴⁸, or R⁵¹⁻⁵⁹ isindependently chosen from (C₁-C₄₀)hydrocarbyl,(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(P))₂,—N(R^(N))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, R^(C)S(O)—, R^(C)S(O)₂—,(R^(C))₂C═N—, R^(C)C(O)O—, R^(C)OC(O)—, R^(C)C(O)N(R^(N))—,(R^(N))₂NC(O)—, halogen, or —H, provided at least one of R¹ or R⁸ is aradical having Formula (II), Formula (III), or Formula (IV).

In Formula (I), each of R²⁻⁴, R⁵⁻⁷, and R⁹⁻¹⁶ is independently selectedfrom (C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃,—Ge(R^(C))₃, —P(R^(P))₂, —N(R^(N))₂—OR^(C), —SR^(C), —NO₂, —CN, —CF₃,R^(C)S(O)—, R^(C)S(O)₂—, (R^(C))₂C═N—, R^(C)C(O)O—, R^(C)OC(O)—,R^(C)C(O)N(R^(N))—, (R^(C))₂NC(O)—, halogen, and —H.

Specific embodiments of catalyst systems will now be described. Itshould be understood that the catalyst systems of this disclosure may beembodied in different forms and should not be construed as limited tothe specific embodiments set forth in this disclosure. Rather,embodiments are provided so that this disclosure will be thorough andcomplete, and will fully convey the scope of the subject matter to thoseskilled in the art.

The term “independently selected” is used herein to indicate that the Rgroups, such as, R¹, R², R³, R⁴, and R⁵ can be identical or different(e.g., R¹, R², R³, R⁴, and R⁵ may all be substituted alkyls or R¹ and R²may be a substituted alkyl and R³ may be an aryl, etc.). Use of thesingular includes use of the plural and vice versa (e.g., a hexanesolvent, includes hexanes). A named R group will generally have thestructure that is recognized in the art as corresponding to R groupshaving that name. These definitions are intended to supplement andillustrate, not preclude, the definitions known to those of skill in theart.

The term “procatalyst” refers to a compound that has catalytic activitywhen combined with an activator. The term “activator” refers to acompound that chemically reacts with a procatalyst in a manner thatconverts the procatalyst to a catalytically active catalyst. As usedherein, the terms “cocatalyst” and “activator” are interchangeableterms.

When used to describe certain carbon atom-containing chemical groups, aparenthetical expression having the form “(C_(x)-C_(y))” means that theunsubstituted form of the chemical group has from x carbon atoms to ycarbon atoms, inclusive of x and y. For example, a (C₁-C₄₀)alkyl is analkyl group having from 1 to 40 carbon atoms in its unsubstituted form.In some embodiments and general structures, certain chemical groups maybe substituted by one or more substituents such as R^(S). An R^(S)substituted version of a chemical group defined using the“(C_(x)-C_(y))” parenthetical may contain more than y carbon atomsdepending on the identity of any groups R^(S). For example, a“(C₁-C₄₀)alkyl substituted with exactly one group R^(S), where R^(S) isphenyl (C₆H₅)” may contain from 7 to 46 carbon atoms. Thus, in generalwhen a chemical group defined using the “(C_(x)-C_(y))” parenthetical issubstituted by one or more carbon atom-containing substituents R^(S),the minimum and maximum total number of carbon atoms of the chemicalgroup is determined by adding to both x and y the combined sum of thenumber of carbon atoms from all of the carbon atom-containingsubstituents R^(S).

In some embodiments, each of the chemical groups (e.g., X, R, etc.) ofthe metal ligand complex of Formula (I) may be unsubstituted having noR^(S) substituents. In other embodiments, at least one of the chemicalgroups of the metal-ligand complex of Formula (I) may independentlycontain one or more than one R^(S). In some embodiments, the sum totalof R^(S) in the chemical groups of the metal-ligand complex of Formula(I) does not exceed 20. In other embodiments, the sum total of R^(S) inthe chemical groups does not exceed 10. For example, if each R¹⁻⁵ wassubstituted with two R^(S), then X and Z cannot be substituted with anR^(S). In another embodiment, the sum total of R^(S) in the chemicalgroups of the metal-ligand complex of Formula (I) may not exceed 5R^(S). When two or more than two R^(S) are bonded to a same chemicalgroup of the metal-ligand complex of Formula (I), each R^(S) isindependently bonded to the same or different carbon atom or heteroatomand may include persubstitution of the chemical group.

The term “substitution” means that at least one hydrogen atom (H) bondedto a carbon atom or heteroatom of a corresponding unsubstituted compoundor functional group is replaced by a substituent (e.g. R^(S)). The term“persubstitution” means that every hydrogen atom (H) bonded to a carbonatom or heteroatom of a corresponding unsubstituted compound orfunctional group is replaced by a substituent (e.g., R^(S)). The term“polysubstitution” means that at least two, but fewer than all, hydrogenatoms bonded to carbon atoms or heteroatoms of a correspondingunsubstituted compound or functional group are replaced by asubstituent.

The term “H” means a hydrogen or hydrogen radical that is covalentlybonded to another atom. “Hydrogen” and “H” are interchangeable andunless clearly specified, mean the same thing.

The term “(C₁-C₄₀)hydrocarbyl” means a hydrocarbon radical of from 1 to40 carbon atoms and the term “(C₁-C₄₀)hydrocarbylene” means ahydrocarbon diradical of from 1 to 40 carbon atoms, in which eachhydrocarbon radical and each hydrocarbon diradical is aromatic ornon-aromatic, saturated or unsaturated, straight chain or branchedchain, cyclic (including mono- and poly-cyclic, fused and non-fusedpolycyclic, including bicyclic; 3 carbon atoms or more) or acyclic andis unsubstituted or substituted by one or more R^(S).

In this disclosure, a (C₁-C₄₀)hydrocarbyl can be an unsubstituted orsubstituted (C₁-C₄₀)alkyl, (C₃-C₄₀)cycloalkyl,(C₃-C₂₀)cycloalkyl-(C₁-C₂₀)alkylene, (C₆-C₄₀)aryl, or(C₆-C₂₀)aryl-(C₁-C₂₀)alkylene. In some embodiments, each of theaforementioned (C₁-C₄₀)hydrocarbyl groups has a maximum of 20 carbonatoms (i.e., (C₁-C₂₀)hydrocarbyl) and other embodiments, a maximum of 12carbon atoms.

The terms “(C₁-C₄₀)alkyl” and “(C₁-C₁₈)alkyl” mean a saturated straightor branched hydrocarbon radical of from 1 to 40 carbon atoms or from 1to 18 carbon atoms, respectively, which is unsubstituted or substitutedby one or more R^(S). Examples of unsubstituted (C₁-C₄₀)alkyl areunsubstituted (C₁-C₂₀)alkyl; unsubstituted (C₁-C₁₀)alkyl; unsubstituted(C₁-C₅)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl;2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl;and 1-decyl. Examples of substituted (C₁-C₄₀)alkyl are substituted(C₁-C₂₀)alkyl, substituted (C₁-C₁₀)alkyl, trifluoromethyl, and[C₄₅]alkyl. The term “[C₄₅]alkyl” (with square brackets) means there isa maximum of 45 carbon atoms in the radical, including substituents, andis, for example, a (C₂₇C₄₀)alkyl substituted by one R^(S), which is a(C₁-C₅)alkyl, respectively. Each (C₁-C₅)alkyl may be methyl,trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

The term “(C₆-C₄₀)aryl” means an unsubstituted or substituted (by one ormore R^(S)) mono-, bi- or tricyclic aromatic hydrocarbon radical of from6 to 40 carbon atoms, of which at least from 6 to 14 of the carbon atomsare aromatic ring carbon atoms, and the mono-, bi- or tricyclic radicalcomprises 1, 2, or 3 rings, respectively; wherein the 1 ring is aromaticand the 2 or 3 rings independently are fused or non-fused and at leastone of the 2 or 3 rings is aromatic. Examples of unsubstituted(C₆-C₄₀)aryl are unsubstituted (C₆-C₂₀) aryl unsubstituted (C₆-C₁₈)aryl;2-(C₁-C₅)alkyl-phenyl; 2,4-bis(C₁-C₅)alkyl-phenyl; phenyl; fluorenyl;tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl;dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examplesof substituted (C₆-C₄₀)aryl are substituted (C₁-C₂₀)aryl; substituted(C₆-C₁₈)aryl; 2,4-bis[(C₂₀)alkyl]-phenyl; polyfluorophenyl;pentafluorophenyl; and fluoren-9-one-1-yl.

The term “(C₃-C₄₀)cycloalkyl” means a saturated cyclic hydrocarbonradical of from 3 to 40 carbon atoms that is unsubstituted orsubstituted by one or more R^(S). Other cycloalkyl groups (e.g.,(C_(x)-C_(y))cycloalkyl) are defined in an analogous manner as havingfrom x to y carbon atoms and being either unsubstituted or substitutedwith one or more R^(S). Examples of unsubstituted (C₃-C₄₀)cycloalkyl areunsubstituted (C₃-C₂₀)cycloalkyl, unsubstituted (C₃-C₁₀)cycloalkyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted(C₃-C₄₀)cycloalkyl are substituted (C₃-C₂₀)cycloalkyl, substituted(C₃-C₁₀)cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

Examples of (C₁-C₄₀)hydrocarbylene include unsubstituted or substituted(C₆-C₄₀)arylene, (C₃-C₄₀)cycloalkylene, and (C₁-C₄₀)alkylene (e.g.,(C₁-C₂₀)alkylene). In some embodiments, the diradicals are on the samecarbon atom (e.g., CH₂) or on adjacent carbon atoms (i.e.,1,2-diradicals), or are spaced apart by one, two, or more than twointervening carbon atoms (e.g., respective 1,3-diradicals,1,4-diradicals, etc.). Some diradicals include α,ω-diradical. Theα,ω-diradical is a diradical that has maximum carbon backbone spacingbetween the radical carbons. Some examples of (C₂-C₂₀)alkyleneα,ω-diradicals include ethan-1,2-diyl (i.e. CH₂CH₂), propan-1,3-diyl(i.e. CH₂CH₂CH₂), 2-methylpropan-1,3-diyl (i.e. CH₂CH(CH₃)CH₂). Someexamples of (C₆-C₄₀)arylene α,ω-diradicals include phenyl-1,4-diyl,napthalen-2,6-diyl, or napthalen-3,7-diyl.

The term “(C₁-C₄₀)alkylene” means a saturated straight chain or branchedchain diradical (i.e., the radicals are not on ring atoms) of from 1 to40 carbon atoms that is unsubstituted or substituted by one or moreR^(S). Examples of unsubstituted (C₁-C₄₀)alkylene are unsubstituted(C₁-C₂₀)alkylene, including unsubstituted —CH₂CH₂—, —(CH₂)₃—, —(CH₂)₄—,—(CH₂)₅—, —(CH₂)₆—, —(CH₂)₇—, —(CH₂)₈—, —CH₂C*HCH₃, and—(CH₂)₄C*(H)(CH₃), in which “C*” denotes a carbon atom from which ahydrogen atom is removed to form a secondary or tertiary alkyl radical.Examples of substituted (C₁-C₄₀)alkylene are substituted(C₁-C₂₀)alkylene, —CF₂—, —C(O)—, and —(CH₂)₁₄C(CH₃)₂(CH₂)₅— (i.e., a6,6-dimethyl substituted normal-1,20-eicosylene). Since as mentionedpreviously two R^(S) may be taken together to form a (C₁-C₁₈)alkylene,examples of substituted (C₁-C₄₀)alkylene also include1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane,2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and2,3-bis(methylene)bicyclo [2.2.2] octane.

The term “(C₃-C₄₀)cycloalkylene” means a cyclic diradical (i.e., theradicals are on ring atoms) of from 3 to 40 carbon atoms that isunsubstituted or substituted by one or more R^(S).

The term “heteroatom,” refers to an atom other than hydrogen or carbon.Examples of groups containing one or more than one heteroatom include O,S, S(O), S(O)₂, Si(R^(C))₂, P(R^(P)), N(R^(N)), —N═C(R^(C))₂,—Ge(R^(C))₂—, or —Si(R^(C))—, where each R^(C) and each R^(P) isunsubstituted (C₁-C₁₈)hydrocarbyl or —H, and where each R^(N) isunsubstituted (C₁-C₁₈)hydrocarbyl. The term “heterohydrocarbon” refersto a molecule or molecular framework in which one or more carbon atomsare replaced with a heteroatom. The term “(C₁-C₄₀)heterohydrocarbyl”means a heterohydrocarbon radical of from 1 to 40 carbon atoms, and theterm “(C₁-C₄₀)heterohydrocarbylene” means a heterohydrocarbon diradicalof from 1 to 40 carbon atoms, and each heterohydrocarbon has one or moreheteroatoms. The radical of the heterohydrocarbyl is on a carbon atom ora heteroatom, and diradicals of the heterohydrocarbyl may be on: (1) oneor two carbon atom, (2) one or two heteroatoms, or (3) a carbon atom anda heteroatom. Each (C₁-C₄₀)heterohydrocarbyl and(C₁-C₄₀)heterohydrocarbylene may be unsubstituted or substituted (by oneor more R^(S)), aromatic or non-aromatic, saturated or unsaturated,straight chain or branched chain, cyclic (including mono- andpoly-cyclic, fused and non-fused polycyclic), or acyclic.

The (C₁-C₄₀)heterohydrocarbyl may be unsubstituted or substituted.Non-limiting examples of the (C₁-C₄₀)heterohydrocarbyl include(C₁-C₄₀)hetero alkyl, (C₁-C₄₀)hydrocarbyl-O—, (C₁-C₄₀)hydrocarbyl-S—,(C₁-C₄₀)hydrocarbyl-S(O)—, (C₁-C₄₀)hydrocarbyl-S(O)₂—,(C₁-C₄₀)hydrocarbyl-Si(R^(C))₂—, (C₁-C₄₀)hydrocarbyl-N(R^(N))—,(C₁-C₄₀)hydrocarbyl-P(R^(P))—, (C₂-C₄₀)heterocycloalkyl,(C₂-C₁₉)heterocycloalkyl-(C₁-C₂₀)alkylene,(C₃-C₂₀)cycloalkyl-(C₁-C₁₉)heteroalkylene,(C₂-C₁₉)heterocycloalkyl-(C₁-C₂₀)heteroalkylene, (C₁-C₅₀)heteroaryl,(C₁-C₁₉)heteroaryl-(C₁-C₂₀)alkylene,(C₆-C₂₀)aryl-(C₁-C₁₉)heteroalkylene, or(C₁-C₁₉)heteroaryl-(C₁-C₂₀)heteroalkylene.

The term “(C₁-C₄₀)heteroaryl” means an unsubstituted or substituted (byone or more R^(S)) mono-, bi- or tricyclic heteroaromatic hydrocarbonradical of from 4 to 40 total carbon atoms and from 1 to 10 heteroatoms,and the mono-, bi- or tricyclic radical comprises 1, 2 or 3 rings,respectively, wherein the 2 or 3 rings independently are fused ornon-fused and at least one of the 2 or 3 rings is heteroaromatic. Otherheteroaryl groups (e.g., (C_(x)-C_(y))heteroaryl generally, such as(C₁-C₁₂)heteroaryl) are defined in an analogous manner as having from xto y carbon atoms (such as 1 to 12 carbon atoms) and being unsubstitutedor substituted by one or more than one R^(S). The monocyclicheteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring.The 5-membered ring has 5 minus h carbon atoms, wherein h is the numberof heteroatoms and may be 1, 2, or 3; and each heteroatom may be O, S,N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicalare pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl;is oxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl;thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl;1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl.The 6-membered ring has 6 minus h carbon atoms, wherein h is the numberof heteroatoms and may be 1 or 2 and the heteroatoms may be N or P.Examples of 6-membered ring heteroaromatic hydrocarbon radical arepyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclicheteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6-ringsystem. Examples of the fused 5,6-ring system bicyclic heteroaromatichydrocarbon radical are indol-1-yl; and benzimidazole-1-yl. Examples ofthe fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radicalare quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatichydrocarbon radical can be a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ringsystem. An example of the fused 5,6,5-ring system is1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of the fused 5,6,6-ringsystem is 1H-benzo[f]indol-1-yl. An example of the fused 6,5,6-ringsystem is 9H-carbazol-9-yl. An example of the fused 6,6,6-ring system isacrydin-9-yl.

The aforementioned heteroalkyl may be saturated straight or branchedchain radicals containing (C₁-C₄₀) carbon atoms, or fewer carbon atomsand one or more of the heteroatoms. Likewise, the heteroalkylene may besaturated straight or branched chain diradicals containing from 1 to 50carbon atoms and one or more than one heteroatoms. The heteroatoms, asdefined above, may include Si(R^(C))₃, Ge(R^(C))₃, Si(R^(C))₂,Ge(R^(C))₂, P(R^(P))₂, P(R^(P)), N(R^(N))₂, N(R^(N)), N, O, OR^(C), S,SR^(C), S(O), and S(O)₂, wherein each of the heteroalkyl andheteroalkylene groups are unsubstituted or substituted by one or moreR^(S).

Examples of unsubstituted (C₂-C₄₀)heterocycloalkyl are unsubstituted(C₂-C₂₀)heterocycloalkyl, unsubstituted (C₂-C₁₀)heterocycloalkyl,aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl,tetrahydrothiophen-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl,hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and2-aza-cyclodecyl.

The term “halogen atom” or “halogen” means the radical of a fluorineatom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). Theterm “halide” means anionic form of the halogen atom: fluoride (F⁻),chloride (Cl⁻), bromide (Br⁻), or iodide (I⁻).

The term “saturated” means lacking carbon-carbon double bonds,carbon-carbon triple bonds, and (in heteroatom-containing groups)carbon-nitrogen, carbon-phosphorous, and carbon-silicon double bonds.Where a saturated chemical group is substituted by one or moresubstituents R^(S), one or more double and/or triple bonds optionallymay or may not be present in substituents R^(S). The term “unsaturated”means containing one or more carbon-carbon double bonds, carbon-carbontriple bonds, and (in heteroatom-containing groups) carbon-nitrogen,carbon-phosphorous, and carbon-silicon double bonds, not including anysuch double bonds that may be present in substituents R^(S), if any, orin (hetero) aromatic rings, if any.

In some embodiments the catalyst systems comprising a metal-ligandcomplex of Formula (I) may be rendered catalytically active by anytechnique known in the art for activating metal-based catalysts ofolefin polymerization reactions. For example, comprising a metal ligandcomplex of Formula (I) may be rendered catalytically active bycontacting the complex to, or combining the complex with, an activatingcocatalyst. Suitable activating cocatalysts for use herein include alkylaluminums; polymeric or oligomeric alumoxanes (also known asaluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating,ion-forming compounds (including the use of such compounds underoxidizing conditions). A suitable activating technique is bulkelectrolysis. Combinations of one or more of the foregoing activatingcocatalysts and techniques are also contemplated. The term “alkylaluminum” means a monoalkyl aluminum dihydride or monoalkylaluminumdihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or atrialkylaluminum. Examples of polymeric or oligomeric alumoxanes includemethylalumoxane, triisobutylaluminum-modified methylalumoxane, andisobutylalumoxane.

Lewis acid activators (cocatalysts) include Group 13 metal compoundscontaining from 1 to 3 (C₁-C₂₀)hydrocarbyl substituents as describedherein. In one embodiment, Group 13 metal compounds aretri((C₁-C₂₀)hydrocarbyl)-substituted-aluminum ortri((C₁-C₂₀)hydrocarbyl)-boron compounds. In other embodiments, Group 13metal compounds are tri(hydrocarbyl)-substituted-aluminum,tri(hydrocarbyl)-boron compounds, tri((C₁-C₁₀)alkyl)aluminum,tri((C₆-C₁₈)aryl)boron compounds, and halogenated (includingperhalogenated) derivatives thereof. In further embodiments, Group 13metal compounds are tris(fluoro-substituted phenyl)boranes,tris(pentafluorophenyl)borane. In some embodiments, the activatingcocatalyst is a tetrakis((C₁-C₂₀)hydrocarbyl borate (e.g. trityltetrafluoroborate) or a tri((C₁-C₂₀)hydrocarbyl)ammoniumtetra((C₁-C₂₀)hydrocarbyl)borane (e.g. bis(octadecyl)methylammoniumtetrakis(pentafluorophenyl)borane). As used herein, the term “ammonium”means a nitrogen cation that is a ((C₁-C₂₀)hydrocarbyl)₄N⁺ a((C₁-C₂₀)hydrocarbyl)₃N(H)⁺, a ((C₁-C₂₀)hydrocarbyl)₂N(H)₂ ⁺,(C₁-C₂₀)hydrocarbyl)₂N(H)₃ ⁺, or N(H)₄ ⁺, wherein each(C₁-C₂₀)hydrocarbyl, when two or more are present, may be the same ordifferent.

Combinations of neutral Lewis acid activators (cocatalysts) includemixtures comprising a combination of a tri((C₁-C₄)alkyl)aluminum and ahalogenated tri((C₆-C₁₈)aryl)boron compound, especially atris(pentafluorophenyl)borane. Other embodiments are combinations ofsuch neutral Lewis acid mixtures with a polymeric or oligomericalumoxane, and combinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane.Ratios of numbers of moles of (metal-ligand complex):(tris(pentafluoro-phenylborane):(alumoxane) [e.g., (Group 4 metal-ligandcomplex):(tris(pentafluoro-phenylborane):(alumoxane)] are from 1:1:1 to1:10:30, in other embodiments, from 1:1:1.5 to 1:5:10.

The catalyst system comprising the metal-ligand complex of Formula (I)may be activated to form an active catalyst composition by combinationwith one or more cocatalysts, for example, a cation forming cocatalyst,a strong Lewis acid, or combinations thereof. Suitable activatingcocatalysts include polymeric or oligomeric aluminoxanes, especiallymethyl aluminoxane, as well as inert, compatible, noncoordinating, ionforming compounds. Exemplary suitable cocatalysts include, but are notlimited to: modified methyl aluminoxane (MMAO), bis(hydrogenated tallowalkyl)methyl tetrakis(pentafluorophenyl)borate(1⁻) amine, andcombinations thereof.

In some embodiments, one or more of the foregoing activating cocatalystsare used in combination with each other. An especially preferredcombination is a mixture of a tri((C₁-C₄)hydrocarbyl)aluminum,tri((C₁-C₄)hydrocarbyl)borane, or an ammonium borate with an oligomericor polymeric alumoxane compound. The ratio of total number of moles ofone or more metal-ligand complexes of Formula (I) to total number ofmoles of one or more of the activating cocatalysts is from 1:10,000 to100:1. In some embodiments, the ratio is at least 1:5000, in some otherembodiments, at least 1:1000; and 10:1 or less, and in some otherembodiments, 1:1 or less. When an alumoxane alone is used as theactivating cocatalyst, preferably the number of moles of the alumoxanethat are employed is at least 100 times the number of moles of themetal-ligand complex of Formula (I). When tris(pentafluorophenyl)boranealone is used as the activating cocatalyst, in some other embodiments,the number of moles of the tris(pentafluorophenyl)borane that areemployed to the total number of moles of one or more metal-ligandcomplexes of Formula (I) from 0.5:1 to 10:1, from 1:1 to 6:1, or from1:1 to 5:1. The remaining activating cocatalysts are generally employedin approximately mole quantities equal to the total mole quantities ofone or more metal-ligand complexes of Formula (I).

The reactivity ratios are determined by the resulting difference inpolymerization rates (i.e., selectivity) between ethylene and the C₃-C₁₂α-olefin with the polymerization catalyst in the polymerization process.It is believed that steric interactions for the polymerization catalystsresult in polymerization of ethylene more selectively than α-olefinssuch as C₃-C₁₂ α-olefins (i.e., the catalyst preferentially polymerizesethylene in the presence of the α-olefin). Again without being bound bytheory, it is believed that such steric interactions cause the catalyst,for example, the homogenous catalyst prepared with or from themetal-ligand complex of Formula (I) to adopt a conformation that allowsethylene to access the M substantially more easily, or adopt a reactiveconformation more readily, or both than the catalyst allows the α-olefinto do so.

For random copolymers in which the identity of the last monomer inserteddictates the rate at which subsequent monomers insert, the terminalcopolymerization model is employed. In this model insertion reactions ofthe type

$\begin{matrix}{{{\ldots\mspace{14mu} M_{i}C^{*}} + M_{j}}\overset{k_{ij}}{\rightarrow}{\ldots\mspace{14mu} M_{i}M_{j}C^{*}}} & \left( {{Equation}\mspace{14mu} 1} \right)\end{matrix}$

where C* represents the catalyst, M_(i) represents monomer i, and k_(ij)is the rate constant having the rate equationR _(P) _(ij) =k _(ij)[ . . . M _(i) C*][M _(j)]  (Equation 2)

The comonomer mole fraction (i=2) in the reaction media is defined bythe equation:

$\begin{matrix}{f_{2} = \frac{\left\lbrack M_{2} \right\rbrack}{\left\lbrack M_{1} \right\rbrack + \left\lbrack M_{2} \right\rbrack}} & \left( {{Equation}\mspace{14mu} 3} \right)\end{matrix}$

A simplified equation for comonomer composition can be derived asdisclosed in George Odian, Principles of Polymerization, Second Edition,John Wiley and Sons, 1970, as follows:

$\begin{matrix}{F_{1} = {{1 - F_{2}} = \frac{{r_{1}\left( {1 - f_{2}} \right)}^{2} + {\left( {1 - f_{2}} \right)f_{2}}}{{r_{1}\left( {1 - f_{2}} \right)}^{2} + {2\left( {1 - f_{2}} \right)f_{2}} + {r_{2}f_{2}^{2}}}}} & \left( {{Equation}\mspace{14mu} 4} \right)\end{matrix}$

From this equation the mole fraction of comonomer in the polymer issolely dependent on the mole fraction of comonomer in the reaction mediaand two temperature dependent reactivity ratios defined in terms of theinsertion rate constants as:

$\begin{matrix}{r_{1} = {{\frac{k_{11}}{k_{12}}\mspace{14mu} r_{2}} = \frac{k_{22}}{k_{21}}}} & \left( {{Equation}\mspace{14mu} 5} \right)\end{matrix}$

For this model as well the polymer composition is a function only oftemperature dependent reactivity ratios and comonomer mole fraction inthe reactor. The same is also true when reverse comonomer or monomerinsertion may occur or in the case of the interpolymerization of morethan two monomers.

Reactivity ratios for use in the foregoing models may be predicted usingwell known theoretical techniques or empirically derived from actualpolymerization data. Suitable theoretical techniques are disclosed, forexample, in B. G. Kyle, Chemical and Process Thermodynamics, ThirdAddition, Prentice-Hall, 1999 and in Redlich-Kwong-Soave (RKS) Equationof State, Chemical Engineering Science, 1972, pp 1197-1203. Commerciallyavailable software programs may be used to assist in deriving reactivityratios from experimentally derived data. One example of such software isAspen Plus from Aspen Technology, Inc., Ten Canal Park, Cambridge, Mass.02141-2201 USA.

Test Methods

Melt Index (I₂) and (I₁₀)

Melt index (I₂) values for the multimodal ethylene-based polymers can bemeasured in accordance to ASTM D1238 at 190° C. at 2.16 kg. Similarly,melt index (I₁₀) values for the multimodal ethylene-based polymers canbe measured in accordance to ASTM D1238 at 190° C. at 10 kg. The valuesare reported in g/10 min, which corresponds to grams eluted per 10minutes. The melt index (I₂) values for the first ethylene-basedcomponent (MI₁), the second ethylene-based component (MI₂), and thethird ethylene-based component (MI₃) can be calculated according toEquation 30 and the methodology described below.

Density

Density measurements for the multimodal ethylene-based polymers can bemade in accordance with ASTM D792, Method B. For the first and secondethylene-based components, the density values can be obtained usingEquation 28 and the methodology described below. For the thirdethylene-based component, the density value can be calculated usingEquation 29.

Conventional Gel Permeation Chromatography (Conventional GPC)

The chromatographic system consisted of a PolymerChar GPC-IR (Valencia,Spain) high temperature GPC chromatograph equipped with an internal IR5infra-red detector (IR5). The autosampler oven compartment was set at160° C. and the column compartment was set at 150° C. The columns usedwere 4 Agilent “Mixed A” 30 cm 20-micron linear mixed-bed. Thechromatographic solvent used was 1,2,4 trichlorobenzene and contained200 ppm of butylated hydroxytoluene (BHT). The solvent source wasnitrogen sparged. The injection volume used was 200 microliters and theflow rate was 1.0 milliliters/minute.

Calibration of the GPC column set was performed with at least 20 narrowmolecular weight distribution polystyrene standards with molecularweights ranging from 580 to 8,400,000 g/mol and were arranged in 6“cocktail” mixtures with at least a decade of separation betweenindividual molecular weights. The standards were purchased from AgilentTechnologies. The polystyrene standards were prepared at 0.025 grams in50 milliliters of solvent for molecular weights equal to or greater than1,000,000 g/mol, and 0.05 grams in 50 milliliters of solvent formolecular weights less than 1,000,000 g/mol. The polystyrene standardswere dissolved at 80° C. with gentle agitation for 30 minutes. Thepolystyrene standard peak molecular weights were converted toethylene-based polymer molecular weights using Equation 6 (as describedin Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):M _(polyethylene) =A×(M _(polystyrene))  (Equation 6)where M is the molecular weight, A has a value of 0.4315 and B is equalto 1.0.

A fifth order polynomial was used to fit the respective ethylene-basedpolymer-equivalent calibration points. A small adjustment to A (fromapproximately 0.39 to 0.44) was made to correct for column resolutionand band-broadening effects such that NIST standard NBS 1475 is obtainedat a molecular weight of 52,000 g/mol.

The total plate count of the GPC column set was performed with Eicosane(prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20minutes with gentle agitation). The plate count (Equation 7) andsymmetry (Equation 8) were measured on a 200 microliter injectionaccording to the following equations:

$\begin{matrix}{{{Plate}\mspace{14mu}{Count}} = {5.54 \times \left( \frac{{RV}_{{Peak}\mspace{14mu}{Max}}}{{Peak}\mspace{14mu}{Width}\mspace{14mu}{at}\mspace{14mu}{half}\mspace{14mu}{height}} \right)^{2}}} & \left( {{Equation}\mspace{14mu} 7} \right)\end{matrix}$where RV is the retention volume in milliliters, the peak width is inmilliliters, the peak max is the maximum height of the peak, and halfheight is one half of the height of the peak maximum.

$\begin{matrix}{{Symmetry} = \frac{\left( {{{Rear}\mspace{14mu}{Peak}\mspace{14mu}{RV}_{{one}\mspace{14mu}{tenth}\mspace{14mu}{height}}} - {RV}_{{Peak}\mspace{14mu}\max}} \right)}{\left( {{RV}_{{Peak}\mspace{14mu}\max} - {{Front}\mspace{14mu}{Peak}\mspace{14mu}{RV}_{{one}\mspace{14mu}{tenth}\mspace{14mu}{height}}}} \right)}} & \left( {{Equation}\mspace{14mu} 8} \right)\end{matrix}$where RV is the retention volume in milliliters and the peak width is inmilliliters, Peak max is the maximum position of the peak, one tenthheight is one tenth of the height of the peak maximum, and where rearpeak refers to the peak tail at later retention volumes than the peakmax and where front peak refers to the peak front at earlier retentionvolumes than the peak max. The plate count for the chromatographicsystem should be greater than 22,000 and symmetry should be between 0.98and 1.22.

Samples were prepared in a semi-automatic manner with the PolymerChar“Instrument Control” Software, wherein the samples were weight-targetedat 2 mg/ml, and the solvent (contained 200 ppm BHT) was added to a prenitrogen-sparged septa-capped vial, via the PolymerChar high temperatureautosampler. The samples were dissolved for 3 hours at 160° C. under“low speed” shaking.

The calculations of M_(n(GPC)), M_(w(GPC)), and M_(z(GPC)) were based onGPC results using the internal IR5 detector (measurement channel) of thePolymerChar GPC-IR chromatograph according to Equations 9-12, usingPolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram ateach equally-spaced data collection point i (IR_(i)) and theethylene-based polymer equivalent molecular weight obtained from thenarrow standard calibration curve for the point i (M_(polyethylene,i) ing/mol) from Equation 6. Subsequently, a GPC molecular weightdistribution (GPC-MWD) plot (wt_(GPC)(lgMW) vs. lgMW plot, wherewt_(GPC)(lgMW) is the weight fraction of ethylene-based polymermolecules with a molecular weight of lgMW) for the ethylene-basedpolymer sample can be obtained. Molecular weight is in g/mol andwt_(GPC)(lgMW) follows the Equation 9.∫wt_(GPC)(lg MW)d lg MW=1.00  (Equation 9)

Number-average molecular weight M_(n(GPC)), weight-average molecularweight M_(w(GPC)) and z-average molecular weight M_(z(GPC)) can becalculated as the following equations.

$\begin{matrix}{M_{n{({GPC})}} = \frac{\sum\limits^{i}{IR}_{i}}{\sum\limits^{i}\left( \frac{{IR}_{i}}{M_{polyethylene},_{i}} \right)}} & \left( {{Equation}\mspace{14mu} 10} \right) \\{M_{w{({GPC})}} = \frac{\sum\limits^{i}\left( {{IR}_{i}*M_{{polyethylene},_{i}}} \right)}{\sum\limits^{i}{IR}_{i}}} & \left( {{Equation}\mspace{14mu} 11} \right) \\{M_{z{({GPC})}} = \frac{\sum\limits^{i}\left( {{IR}_{i}*M_{{polyethylene},_{i}^{2}}} \right)}{\sum\limits^{i}\left( {{IR}_{i}*M_{{polyethylene},_{i}}} \right)}} & \left( {{Equation}\mspace{14mu} 12} \right)\end{matrix}$

In order to monitor the deviations over time, a flow rate marker(decane) was introduced into each sample via a micropump controlled withthe PolymerChar GPC-IR system. This flow rate marker (FM) was used tolinearly correct the pump flow rate (Flowrate(nominal)) for each sampleby RV alignment of the respective decane peak within the sample (RV(FMSample)) to that of the decane peak within the narrow standardscalibration (RV(FM Calibrated)). Any changes in the time of the decanemarker peak are then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run. To facilitate the highestaccuracy of a RV measurement of the flow marker peak, a least-squaresfitting routine is used to fit the peak of the flow marker concentrationchromatogram to a quadratic equation. The first derivative of thequadratic equation is then used to solve for the true peak position.After calibrating the system based on a flow marker peak, the effectiveflow rate (with respect to the narrow standards calibration) iscalculated as Equation 13. Processing of the flow marker peak was donevia the PolymerChar GPCOne™ Software. Acceptable flow rate correction issuch that the effective flowrate should be within 0.5% of the nominalflowrate.Flow rate_(effective)=Flow rate_(nominal)×(RV(FM _(calibrated))/RV(FM_(sample)))  (Equation 13)

IR5 GPC Comonomer Content (GPC-CC) Plot

A calibration for the IR5 detector ratioing was performed using at leastten ethylene-based polymer standards (ethylene-based polymer homopolymerand ethylene/octene copolymers) of known short chain branching (SCB)frequency (The comonomer content of the reference materials isdetermined using 13C NMR analysis in accordance with techniquesdescribed, for example, in U.S. Pat. No. 5,292,845 (Kawasaki, et al.)and by J. C. Randall in Rev. Macromol. Chem. Phys., C29, 201-317a, whichare incorporated herein by reference), ranging from homopolymer (0SCB/1000 total C) to approximately 50 SCB/1000 total C, where total C isequal to the carbons in backbone plus the carbons in branches. Eachstandard had a weight-average molecular weight from 36,000 g/mole to126,000 g/mole and had a molecular weight distribution from 2.0 to 2.5,as determined by GPC. Typical Copolymer Standards properties andmeasurements are shown in Table A.

TABLE A “Copolymer” Standards Wt % lR5 SCB/1000 M_(w(GPC)) M_(W(GPC))/Comonomer Area ratio Total C g/mol M_(n(GPC)) 0.0 0.1809 0.0 38,400 2.201.1 0.1810 1.4 107,000 2.09 5.4 0.1959 6.8 37,400 2.16 8.6 0.2043 10.836,800 2.20 9.4 0.2031 11.8 103,200 2.26 14.0 0.2152 17.5 36,000 2.1914.3 0.2161 17.9 103,600 2.20 23.1 0.2411 28.9 37,300 2.22 35.9 0.270844.9 42,200 2.18 39.2 0.2770 49.0 125,600 2.22

The “IR5 Area Ratio (or“IR5_(Methyl Channel Area)/IR5_(Measurement Channel Area)”)” of “thebaseline-subtracted area response of the IR5 methyl channel sensor” to“the baseline-subtracted area response of IR5 measurement channelsensor” (standard filters and filter wheel as supplied by PolymerChar:Part Number IR5_FWM01 included as part of the GPC-IR instrument) wascalculated for each of the “Copolymer” standards. A linear fit of the Wt% Comonomer versus the “IR5 Area Ratio” was constructed in the form ofthe following Equation 14:wt % Comonomer=A ₀+[A ₁(IR5_(Methyl Channel Area)/IR5_(Measurement Channel Area))]  (Equation 14)

Therefore, a GPC-CC (GPC-Comonomer Content) plot (wt % comonomer vs.lgMW) can be obtained. End-Group Correction of the wt % Comonomer datacan be made via knowledge of the termination mechanism if there issignificant spectral overlap with the comonomer termination (methyls)via the molecular weight determined at each chromatographic slice.

Crystallization Elution Fractionation (CEF)

Comonomer distribution analysis, also commonly called short chainbranching distribution (SCBD), is measured with Crystallization ElutionFractionation (CEF) (PolymerChar, Spain) (Monrabal et al, Macromol.Symp. 257, 71-79 (2007), which is incorporated herein by reference)equipped with an IR (IR-4 or IR-5) detector (PolymerChar, Spain) and2-angle light scattering detector Model 2040 (Precision Detectors,currently Agilent Technologies). Distilled anhydrousortho-dichlorobenzene (ODCB) with 600 ppm antioxidant butylatedhydroxytoluene (BHT) was used as solvent. For the autosampler with thecapability of N₂ purge, no BHT was added. A GPC guard column (20microns, or 10 microns, 50×7.5 mm) (Agilent Technologies) is installedjust before the IR detector in the detector oven. Sample preparation isdone with an autosampler at 160° C. for 2 hours under shaking at 4 mg/ml(unless otherwise specified). The injection volume is 300 μl. Thetemperature profile of CEF is: crystallization at 3° C./min from 110° C.to 30° C., the thermal equilibrium at 30° C. for 5 minutes, elution at3° C./min from 30° C. to 140° C. The flow rate during crystallizationwas at 0.052 ml/min. The flow rate during elution is at 0.50 ml/min. Thedata was collected at one data point/second.

The CEF column is packed by The Dow Chemical Company with glass beads at125 μm±6% (MO-SCI Specialty Products) with ⅛-inch stainless tubing.Glass beads are acid washed by MO-SCI Specialty by request from The DowChemical Company. Column volume is 2.06 ml. Column temperaturecalibration was performed by using a mixture of NIST Standard ReferenceMaterial Linear ethylene-based polymer 1475a (1.0 mg/ml) and Eicosane (2mg/ml) in ODCB. Temperature was calibrated by adjusting elution heatingrate so that NIST linear ethylene-based polymer 1475a has a peaktemperature at 101.0° C., and Eicosane has a peak temperature of 30.0°C. The CEF column resolution was calculated with a mixture of NISTlinear ethylene-based polymer 1475a (1.0 mg/ml) and hexacontane (Fluka,purum ≥97.0%, 1 mg/ml). A baseline separation of hexacontane and NISTethylene-based polymer 1475a was achieved. The area of hexacontane (from35.0 to 67.0° C.) to the area of NIST 1475a from 67.0 to 110.0° C. is 50to 50, the amount of soluble fraction below 35.0° C. is less than 1.8 wt%. The CEF column resolution is defined in Equation 15:

$\begin{matrix}{{Resolution} = {\frac{{{Peak}\mspace{14mu}{Temperature}_{{NIST}\mspace{14mu} 1475A}} - {{Peak}\mspace{14mu}{Temperature}_{Hexacontane}}}{{{Width}\mspace{14mu}{at}\mspace{14mu}{Half}\mspace{14mu}{Height}_{{NIST}\mspace{14mu} 1475A}} + {{Width}\mspace{14mu}{at}\mspace{14mu}{Half}\mspace{14mu}{Height}_{Hexacontane}}} \geq 6.0}} & \left( {{Equation}\mspace{14mu} 15} \right)\end{matrix}$where the half height width is measured in temperature and resolution isat least 6.0.

The CEF instrument was equipped with an Agilent (Santa Clara, Calif.)Model 2040 2-angle light scattering detector, and the light scatteringwas calibrated using the 90 degree signal channel with a knownhomopolymer ethylene-based polymer standard of known molecular weight(approximately 120,000 g/mol). The IR (infrared) detector was alsocalibrated for mass response. Molecular weight (M_(w(CEF))) at eachelution point was calculated as a function of elution temperature inregions of adequate signal to noise. Area calculations (representing thetotal area of the 90 degree light scattering signal divided by therespective IR area and factored by the respective detector constants)was used to evaluate the weight-average molecular weight across regionsof the elution temperature and to obtain a CEF-MW plot (M_(w(CEF)) vs.temperature curve). The area calculations have an inherent advantage ofsignal to noise over the continuous calculations. Both the IR and LS(light scattering) signals were subtracted from their baseline signallevels in accordance with normal chromatographic integration techniques.

A calculation of the “Critical Temperature (T_(critical)),” the weightfraction of polymer and the weight-average molecular weight in thetemperature range of up to and including the critical temperature(M_(w(CEF)) of CEF fraction between 20° C. and T_(critical)) wereobtained as follows:

Obtain a CEF-SCBD (CEF-short chain branching distribution) plot usingweight fraction (wt_(CEF)(T)) at each temperature (T) from 20.0° C. to119.9° C. with a temperature step increase of 0.2° C., where∫_(20.0) ^(119.9) wt_(CEF)(T)dT=1.00  (Equation 16)

Critical temperature is defined by the density of the resin (in g/cc)according toT _(critical)(° C.)=1108.1(° C.·cc/g)×density(g/cc)−952.1(°C.)  (Equation 17)

CEF weight fraction between 20° C. to T_(critical) is calculated fromCEF-SCBD as∫_(20.0) ^(T) ^(critical) wt_(CEF)(T)dT  (Equation 18)

Similarly, the weight-average molecular weight of the fraction from 20°C. up to and including the critical temperature (M_(w(CEF)) of CEFfraction between 20° C. and T_(critical)) was calculated as the arearatio of the sum of the 90 degree light scattering responses divided bythe sum of the IR detector responses between 20° C. to T_(critical) andfactored for the calibrated detector constants. The molecular weightcalculations and calibrations were performed in GPCOne® software.

Numerical Deconvolution of Bivariate Data

Numerical Deconvolution of Bivariate Data is used to obtain the density,molecular weight, and melt index (I₂) of the first ethylene-basedcomponent, the second ethylene-based component, and the thirdethylene-based component. Numerical deconvolution of the combinedCEF-SCBD (wt_(CEF)(T) vs. temperature (T) plot from CEF) and GPC-MWD(wt_(GPC)(lgMW)) vs. lgMW plot from conventional GPC) data was performedusing Microsoft Excel® Solver (2013). For CEF-SCBD, the calculatedweight fraction (wt_(sumCEF)(T)) versus temperature (T) data obtainedusing the method described in the CEF section (in the range ofapproximately 23 to 120° C.) was quelled to approximately 200equally-spaced data points in order for a balance of appropriateiterative speed and temperature resolution. A single or series (up to 3peaks for each component) of Exponentially-Modified GaussianDistributions (Equation 19) were summed to represent each component(wt_(C,CEF)(T)), and the components were summed to yield the totalweight (wt_(sum,CEF)(T)) at any temperature (T) as shown in Equations20A-D.

$\begin{matrix}{y_{T,C,P} = {\frac{a_{0,C,P}}{2a_{3,C,P}}{e^{({\frac{a_{2,C,P}^{2}}{2a_{3,C,P}^{2}} + \frac{a_{1,C,P} - T}{a_{3,C,P}}})}\left\lbrack {\frac{1}{2} + {\frac{1}{2}{{erf}\left( {\frac{T - a_{1,C,P}}{\sqrt{2}a_{2,C,P}} - \frac{a_{2,C,P}}{\sqrt{2}a_{3,C,P}}} \right)}}} \right\rbrack}}} & \left( {{Equation}\mspace{14mu} 19} \right)\end{matrix}$where C means component (C=1, 2 or 3), P means peak (P=1, 2, or 3),a_(0,C,P) is the chromatographic area in ° C. for the P-th peak of theC-th component, a_(1,C,P) is the peak center in ° C. for the P-th peakof the C-th component, a_(2,C,P) is the peak width in ° C. for the P-thpeak of the C-th component, a_(3,C,P) is the peak tailing in ° C. forthe P-th peak of the C-th component, and T is the elution temperature in° C. In the case of a single Exponentially-Modified GaussianDistributions is used to represent the CEF-SCBD of a component,y_(T,C,2)=y_(T,C,3)=0. In the case of two Exponentially-ModifiedGaussian Distributions are used to represent the CEF-SCBD of acomponent, only y_(T,C,3)=0.wt_(C1,CEF)(T)=Σ_(p=1) ³ y _(T,1,P)  (Equation 20A)wt_(C2,CEF)(T)=Σ_(p=1) ³ y _(T,2,P)  (Equation 20B)wt_(C3,CEF)(T)=Σ_(p=1) ³ y _(T,3,P)  (Equation 20C)wt_(sum,CEF)(T)=wt_(C1,CEF)(T)+wt_(C2,CEF)(T)+wt_(C3,CEF)(T)  (Equation20D)

Weight fraction of each component (wf_(cEF)) from CEF-SCBD deconvolutioncan be expressed bywf _(C1,CEF)=∫wt_(C1)(T)dT  (Equation 21A)wf _(C2,CEF)=∫wt_(C2)(T)dT  (Equation 21B)wf _(C3,CEF)=∫wt_(C3)(T)dT  (Equation 21C)wt_(sum,CEF)(T)dT=1.00  (Equation 21D)where wf_(C1,CEF) is the weight fraction of the first ethylene-basedcomponent obtained from CEF-SCBD deconvolution, wf_(C2,CEF) is theweight fraction of the second ethylene-based component obtained fromCEF-SCBD deconvolution, wf_(C3,CEF) is the weight fraction of the thirdethylene-based component obtained from CEF-SCBD deconvolution, and thesum of the fractions is normalized to 1.00.

For GPC-MWD, the MWD obtained by the Conventional GPC descriptionsection was imported into the same spreadsheet in 0.01 lg(MW/(g/mol))increments between 2.00 and 7.00 (501 data points total). A Flory-SchulzDistribution with a weight-average molecular weight of M_(w,Target) anda polydispersity (M_(w)/M_(n)) of 2.0 is shown in the followingequations.

$\begin{matrix}{\mspace{79mu}{{wt}_{{F - S},i} = {\left( \frac{3.03485 \times M_{i}}{M_{w,{Target}}} \right)^{2} \times e^{(\frac{{- 2}M_{i}}{M_{w,{Target}}})}}}} & \left( {{Equation}\mspace{14mu} 22} \right) \\{\left. {\left. {\sum_{i = 0}^{499}{{wt}_{{F - S},i} \times {\lg\left( {M_{i + 1}\text{/}g\text{/}{mol}} \right)}}} \right) - {\lg\left( {M_{i}\text{/}\left( {g\text{/}{mol}} \right)} \right)}} \right) = 1.00} & \left( {{Equation}\mspace{14mu} 23} \right) \\{\mspace{79mu}{{{\lg\left( {M_{i + 1}\text{/}\left( {g\text{/}{mol}} \right)} \right)} - {\lg\left( {M_{i}\text{/}\left( {g\text{/}{mol}} \right)} \right)}} = 0.01}} & \left( {{Equation}\mspace{14mu} 24} \right)\end{matrix}$where wt_(F-S,i) is the weigh fraction of the molecules atlg(M_(i)/(g/mol)) (M_(i) in g/mol), i is integers ranging from 0 to 500to represent each data point on the GPC-MWD plot and correspondinglg(M_(i)/(g/mol)) is 2+0.01×i.

The Flory-Schulz Distribution is subsequently broadened using a sum of aseries normal distribution at each lg(M_(i)/(g/mol)). The weightfraction of the Normal Distribution with its peak value atlg(M_(i)/(g/mol)) is kept the same as the original Flory-SchulzDistribution. The broadened Flory-Schulz Distribution curve can bedescribed as the following equation.

$\begin{matrix}{\left. {{wt}_{GPC}\left( {\lg\left( {M_{i}\text{/}g\text{/}{mol}} \right)} \right)} \right) = {\sum_{j = 0}^{500}{\frac{{wt}_{{F - S},j}}{\sqrt{2\;\pi}\sigma}e^{- \frac{{({{\lg{({M_{i}\text{/}{({g\text{/}{mol}})}})}} - {({2 + {0.01 \times j}})}})}^{2}}{2\;\sigma^{2}}}}}} & \left( {{Equation}\mspace{14mu} 25} \right)\end{matrix}$where wt_(GPC)(lg(M_(i)/(g/mol))) is the weight fraction of themolecules at lg(M_(i)/(g/mol)), j is integers ranging from 0 to 500, σis the standard deviation of the Normal Distribution. Therefore,molecular weight distribution curves for all three components can beexpressed as the following equations. Number-average molecular weight(M_(n(GPC))), weight-average molecular weight (M_(w(GPC))), and MWD(M_(w(GPC))/M_(n(GPC))) can be calculated from the broadenedFlory-Schulz Distribution.

$\begin{matrix}{{{wt}_{{C\; 1},{GPC}}\left( {\lg\left( {M_{i}\text{/}\left( {g\text{/}{mol}} \right)} \right)} \right)} = {{wf}_{{C\; 1},{GPC}} \times {\sum_{j = 0}^{500}{\frac{{wt}_{{F - S},{C\; 1},j}}{\sqrt{2\;\pi}\sigma_{C\; 1}}e^{- \frac{{({{\lg{({M_{i}\text{/}{({g\text{/}{mol}})}})}} - {({2 + {0.01 \times j}})}})}^{2}}{2\;\sigma_{C\; 1}^{2}}}}}}} & \left( {{Equation}\mspace{14mu} 26A} \right) \\{{{wt}_{{C\; 2},{GPC}}\left( {\lg\left( {M_{i}\text{/}\left( {g\text{/}{mol}} \right)} \right)} \right)} = {{wf}_{{C\; 2},{GPC}} \times {\sum_{j = 0}^{500}{\frac{{wt}_{{F - S},{C\; 2},j}}{\sqrt{2\;\pi}\sigma_{C\; 2}}e^{- \frac{{({{\lg{({M_{i}\text{/}{({g\text{/}{mol}})}})}} - {({2 + {0.01 \times j}})}})}^{2}}{2\;\sigma_{C\; 2}^{2}}}}}}} & \left( {{Equation}\mspace{14mu} 26B} \right) \\{{{wt}_{{C\; 3},{GPC}}\left( {\lg\left( {M_{i}\text{/}\left( {g\text{/}{mol}} \right)} \right)} \right)} = {{wf}_{{C\; 3},{GPC}} \times {\sum_{j = 0}^{500}{\frac{{wt}_{{F - S},{C\; 3},j}}{\sqrt{2\;\pi}\sigma_{C\; 3}}e^{- \frac{{({{\lg{({M_{i}\text{/}{({g\text{/}{mol}})}})}} - {({2 + {0.01 \times j}})}})}^{2}}{2\;\sigma_{C\; 3}^{2}}}}}}} & \left( {{Equation}\mspace{14mu} 26C} \right) \\{{{wt}_{{sum},{GPC}}\left( {\lg\left( {M_{i}\text{/}\left( {g\text{/}{mol}} \right)} \right)} \right)} = {{{wt}_{{C\; 1},{GPC}}\left( {\lg\left( {M_{i}\text{/}\left( {g\text{/}{mol}} \right)} \right)} \right)} + {{wt}_{{C\; 2},{GPC}}\left( {\lg\left( {M_{i}\text{/}\left( {g\text{/}{mol}} \right)} \right)} \right)} + {{wt}_{{C\; 3},{GPC}}\left( {\lg\left( {M_{i}\text{/}\left( {g\text{/}{mol}} \right)} \right)} \right)}}} & \left( {{Equation}\mspace{14mu} 26D} \right)\end{matrix}$where σ is the normal distribution width parameter, the subscripts C1,C2 and C3 represent the first, the second and the third ethylene-basedcomponents, respectively, wf_(C1,GPC), wf_(C2,GPC) and wf_(C3,GPC) arethe weight fractions of the first, the second and the thirdethylene-based components from GPC-MWD, respectively.

Each of the paired components (the first ethylene-based component (C1),the second ethylene-based component (C2), and third ethylene-basedcomponent (C3)) from CEF-SCBD and GPC-MWD are considered equivalentmasses for their respective techniques as shown in Equations 27A-E.wf _(C1,CEF) +wf _(C2,CEF) +wf _(C3,CEF)=1.00  (Equation 27A)wf _(C1,CEF) +wf _(C2,CEF) +wf _(C3,CEF)=1.00  (Equation 27B)wf _(C1,CEF) =wf _(C1,GPC)  (Equation 27C)wf _(C2,CEF) =wf _(C2,GPC)  (Equation 27D)wf _(C2,CEF) =wf _(C2,GPC)  (Equation 27E)

Process and catalyst data, including catalysts efficiency and reactormass balance, can be leveraged for initial estimates of the relativeweight production of each component. Alternatively, initial estimates ofthe weight fraction for each component can be compared by integratingpartial areas of the CEF-SCBD or GPC-MWD plot of the multimodalethylene-based polymer, especially noting visible areas with definedpeaks or peak inflection points. For example, the peak area for eachcomponent in CEF-SCBD curve, if well-separated may be estimated bydropping vertical lines between peaks. Association of the molecularweight order and initial estimation of the molecular weight may beobtained from the peak positions of the associated component areas inthe CEF-SCBD and CEF-MW plots and agreement should be expected with theGPC-CC measurements. In some cases, initial assignment of peak areas andcomposition may be obtained from a multi-modal GPC-MWD as the startingpoint and validated under the CEF-SCBD and CEF-MW plots.

Initial estimates of the peak width and tailing in CEF-SCBD for eachcomponent can be obtained from a calibration of peak width vs.temperature using a series of standard single-site samples such as thosepreviously presented in Table A.

Microsoft Excel® Solver is programmed to minimize the combined sum ofsquares of residuals between the wt_(sum,GPC)(lgM_(i)) and the measuredGPC-MWD, and sum of squares of residuals between the wt_(sum,CEF)(T) andthe measured CEF-SCBD (wherein the sampling width and areas of the twoobserved distributions are normalized in regards to each other). Thereis equal weighting given to the GPC-MWD and CEF-SCBD fit as they aresimultaneously converged. Initial estimated values for weight fractionand peak width in CEF-SCBD as well as molecular weight target for eachcomponent are used for the Microsoft Excel® Solver to begin with asdescribed herein.

Co-crystallization effects which distort peak shape in CEF arecompensated for by the use of the Exponentially-Modified Gaussian (EMG)peak fit and in extreme cases, the use of multiple (up to 3) EMG peakssummed to describe a single component. A component produced via a singlesite catalyst may be modeled by a single EMG peak. A component producedvia a Ziegler-Natta catalyst may be modeled by 1, 2, or 3 EMG peaks, ora single EMG peak possessing a long low temperature-facing tailsufficing for a Ziegler-Natta component of very high density, very lowmolecular weight targets on the CEF-SCBD plot. In all cases, only asingle broadened Flory-Schulz distribution (Equation 26A-C) is used withthe weight fraction assigned as the associated sum of one or more of theEMG components from the CEF-SCBD model (Equations 27A-E).

The GPC deconvolution is constrained with a normal distribution widthparameter (σ_(C1) or σ_(C2)) from Equation 26A, 26B between 0.000 and0.170 (corresponding polydispersities of approximately 2.00 to 2.33) forthe first and second ethylene-based components which are made via singlesite catalysts. The M_(w,Target) in Equation 22 is constrained to belowest for the third ethylene-ethylene based component in these cases,since it is targeted to be the lowest from this specific reactionscheme. Note that it is not constrained by definition to be lowest inall possible cases, depending upon the desired performance target of thecombined resin in-reactor blend. The ranking (preliminary estimation) ofthe two weight-average molecular weights (M_(w,Target)) of the firstethylene-based component and the second ethylene-based component isobserved by the M_(w(CEF)) from the CEF-MW plot (M_(w(CEF)) vs.temperature curve) at the temperatures at which the first and secondethylene-based component peaks are observed on the CEF-SCBD plot(wt_(CEF)(T) vs. temperature curve). Therefore, the order of themolecular weights for the three components is well-known. A reactor massbalance yields the percentage mass (wf) of Equation 26C of the thirdethylene-based component, or alternatively it can be calculated from thedeconvolution using Equation 26D, depending upon the strength of theknown distribution models for CEF and GPC and the total weight fractionmust sum to unity (Equations 27A-E).

In general, it has been found that approximately 20 solver iterationswill typically reach good convergence on the solution using Excel®. Ifthere is a disagreement in order of the peaks versus measured molecularweight by the CEF-MW plot and the observed comonomer wt % measurementmeasured via GPC-CC, then the data must be reconciled by changing theiteration starting points (temperature or lgMW) in Excel or changing thewidth and tail factors slightly such that the iteration will proceedwith convergence to a consistent solution amongst the measurements, orthe resolution of the measurements must be increased, or an additionalpeak may be added to the CEF-SCBD to better approximate the elution peakshape of the individual components. Such components could be modeleda-priori via several EMG distributions if they are preparedindividually.

Additionally a predicted M_(w(CEF)) response for CEF-MW may be generatedby using the weight-average molecular weight by GPC-MWD of each of thecomponents multiplied by the observed weight fraction of each of thecomponents at each point along the CEF-SCBD plot. The predictedM_(w(CEF)) needs to be in agreement with the measured M_(w(CEF)) in theCEF-MW plot. By plotting comonomer incorporation as a function ofelution temperature based on a series of known copolymer standards, theGPC-CC plot can also be predicted using the measured M_(w(CEF)) andcomonomer incorporation of individual component from CEF-MW and CEF-SCBDplots. The predicted GPC-CC plot needs to be in agreement with themeasured GPC-CC.

A peak temperature vs. density correlation for the CEF-SCBD data isobtained using a series of linear ethylene-based polymer standard resinspolymerized from single site catalysts of approximately 1 g/10 min meltindex (I₂), or nominal weight-average molecular weight of approximately105,000 g/mol by GPC, and polydispersities (or MWD) of less than 2.3 byGPC. At least 10 standard resins of known comonomer content, density,and molecular weight within the density range of 0.87 to 0.96 g/cc areused. Peak temperature and density data are fit with a 5th orderpolynomial curve to obtain the calibration curve.

A peak width and peak tail vs. peak temperature correlation is obtainedsimilarly by fitting the peak width and peak tail vs. temperature of theabove resins with a linear line, which is very useful for initialestimates in the deconvolution process.

The first ethylene-based component and the second ethylene-basedcomponent were noted in the resins presented herein directly from theCEF-SCBD deconvolution plot as the first two peaks between 35° C. and90° C. elution temperature. A “Raw Density” (Density_(Raw)) wascalculated from these observed peak positions using the calibrationcurve of peak temperature vs. density. The Density_(Raw) (in g/cc) wascorrected to Density_(True) (in g/cc) accounting for molecular weight(in g/mol) contributions by using the Equation 28:Density_(True)=Density_(Raw)−0.254 g/cc×[lg(M_(w(GPC))/(g/mol))−5.02]  (Equation 28)where M_(w(GPC)) is the weight-average molecular weight of the singlecomponent deconvoluted from GPC-MWD.

The density of the third ethylene-based component may be calculatedbased on the known density of the resin, Density_(True) of the firstethylene-based component, Density_(True) of the second ethylene-basedcomponent, and the weight fractions of each components according to thefollowing Equation 29.

$\begin{matrix}{\frac{1}{{Density}_{measured}} = {\frac{{weight}\mspace{14mu}{fraction}\mspace{14mu}{of}\mspace{14mu} 1{st}\mspace{14mu}{ethylene}\mspace{14mu}{based}\mspace{14mu}{component}}{{Density}_{True}\mspace{14mu}{of}\mspace{14mu} 1{st}\mspace{14mu}{ethylene}\mspace{14mu}{based}\mspace{14mu}{component}} + \frac{{weight}\mspace{14mu}{fraction}\mspace{14mu}{of}\mspace{14mu} 2{nd}\mspace{14mu}{ethylene}\mspace{14mu}{based}\mspace{14mu}{component}}{{Density}_{True}\mspace{14mu}{of}\mspace{14mu} 2{nd}\mspace{14mu}{ethylene}\mspace{14mu}{based}\mspace{14mu}{component}} + \frac{{weight}\mspace{14mu}{fraction}\mspace{14mu}{of}\mspace{14mu} 3{rd}\mspace{14mu}{ethylene}\mspace{14mu}{based}\mspace{14mu}{component}}{{density}\mspace{14mu}{of}\mspace{14mu} 3{rd}\mspace{14mu}{ethylene}\mspace{14mu}{based}\mspace{14mu}{component}}}} & \left( {{Equation}\mspace{14mu} 29} \right)\end{matrix}$

The melt index (I₂) of each ethylene-based component may be estimatedfrom their weight-average molecular weight by the following equation:lg(I ₂/(g/10 min))=−3.759×lg(M _(w(GPC))/(g/mol))+18.9  (Equation 30)where M_(w(GPC)) is the weight average molecular weight (in g/mol) ofthe single component deconvoluted from GPC-MWD curve and I₂ is the meltindex in (g/10 min). Note that the amount of long chain branching maychange the coefficients.

Moreover, for the determination of product composition, direct samplingof a single reactor with a single catalyst with the same reactorconditions, a first reactor sampling for a series dual-reactorconfiguration, or sampling of both reactors for a parallel dual-reactorconfiguration may be used to aid in the determination of the density,melt index (I₂), GPC-MWD, and CEF-SCBD of each individual component ofthe multimodal ethylene-based polymer, especially providing that thereaction is effectively killed past the sampling point. This allowsbetter confirmation in cases wherein the first and second ethylene-basedcomponent peak positions cannot adequately be determined from the3-component mixture.

Direct examination and quantitation by analytical cross-fractionation inGPC-TREF, such as the PolymerChar CFC unit (Valencia, Spain) equippedwith on-line light scattering and employing similar calibrations inbivariate space representing SCBD and molecular weight and calibratingthe relationship to density may be used to measure amounts ordiscriminate more precisely of each of the components as well,especially for the initial estimates or in cases that may produce highco-crystallization or low resolution/discrimination of speciesparticularly in both MWD and SCBD space. (Development of an AutomatedCross-Fractionation Apparatus (TREF-GPC) for a Full Characterization ofthe Bivariate Distribution of Polyolefins. Polyolefin Characterization.Macromolecular Symposia, Volume 257, 2007, Pages 13-28. A. Oran, B.Monrabal, J. Sancho-Tello). Adequate resolution must be obtained in bothlgMW and temperature space and verification should be done through bothdirect compositional ratioing, for example, IR-5 and light scatteringmolecular weight measurement. See Characterization of ChemicalComposition along the Molar Mass Distribution in Polyolefin Copolymersby GPC Using a Modern Filter-Based IR Detector. PolyolefinCharacterization—ICPC 2012 Macromolecular Symposia Volume 330, 2013,Pages 63-80, A. Ortín, J. Montesinos, E. López, P. del Hierro, B.Monrabal, J. R. Torres-Lapasió, M. C. García-Álvarez-Coque.Deconvolution of the components must use a similar set of equations andanalogous calibration verified by a series of single-site resins andresin blends.

EXAMPLES

The following examples illustrate features of the present disclosure butare not intended to limit the scope of the disclosure.

Comparative Examples 1 and 2

As described below, Comparative Examples 1 and 2 illustrate thesynthesis of a trimodal polymer from a two reactor, three catalystsystem. Specifically, the trimodal polymers produced through the tworeactor, three catalyst system was produced in accordance with theprocess conditions provided in Table 1 as follows.

In the dual series reactor configuration, the effluent from the firstpolymerization reactor (containing solvent, monomer, comonomer,hydrogen, catalyst components, and dissolved polymer) exits the firstreactor and is added to the second reactor separate from the other feedsto the second reactor. The dual series reactor system consisted of twoliquid full, adiabatic, continuously stirred tank reactors (CSTRs).

Following catalyst deactivation and additive addition, the reactoreffluent entered a devolatilization system where the polymer was removedfrom the non-polymer stream. The non-polymer stream was removed from thesystem. The isolated polymer melt was pelletized and collected.

All raw materials (monomer and comonomer) and the process solvent (anarrow boiling range high-purity paraffinic solvent, ISOPAR E) werepurified with molecular sieves before introduction into the reactionenvironment. Hydrogen was supplied pressurized as a high purity gradeand was not further purified. The reactor monomer feed stream waspressurized via a mechanical compressor to above reaction pressure. Thesolvent feed was pressurized via a pump to above reaction pressure. Thecomonomer feed was pressurized via a pump to above reaction pressure.The individual catalyst components were manually batch diluted tospecified component concentrations with purified solvent and pressurizedto above reaction pressure. All reaction feed flows were measured withmass flow meters and independently controlled with metering pumps.

Independent control of all fresh solvent, monomer, comonomer, hydrogen,and catalyst component feeds to each reactor was utilized. The totalfresh feed streams to each reactor (solvent, monomer, comonomer, andhydrogen) were temperature controlled by passing the feed stream througha heat exchanger. The total fresh feed to each polymerization reactorwas injected into the reactor in one or more locations. The catalystcomponents were injected into the polymerization reactor separate fromthe other feeds. An agitator in a CSTR reactor was responsible forcontinuous mixing of the reactants. Oil bath (for a CSTR reactor)provided fine tuning of the reactor temperature control.

For the reactor utilizing dual primary catalysts in one reactor, twocalculated variables are controlled: (1) the total mass flow of primarycatalyst 1 and primary catalyst 2, and (2) the mass fraction for primarycatalyst 1 out of the total mass flow of both primary catalysts. Thetotal mass flow of both primary catalysts was computer controlled tomaintain the individual reactor monomer conversion at the specifiedtarget. The mass fraction of primary catalyst 1 was controlled tomaintain the relative mass fraction of polymer produced by each catalystin that individual reactor. The cocatalyst components for the reactorutilizing dual primary catalysts were fed based on calculated specifiedmolar ratios to the total of both primary catalyst components.

TABLE 1 Comparative Comparative Example 1 Example 2 ReactorConfiguration Type Dual Series Dual Series Comonomer type Type 1-octene1-octene First Reactor Feed Solvent/Ethylene g/g 8.1 8.1 Mass Flow RatioFirst Reactor Feed Comonomer/Ethylene g/g 0.57 0.59 Mass Flow RatioFirst Reactor Feed Hydrogen/Ethylene g/g 2.91E-04 3.50E-04 Mass FlowRatio First Reactor Temperature ° C. 150 150 First Reactor Pressure barg28 28 First Reactor Ethylene Conversion % 77.1 77.0 First ReactorCatalyst 1 Type Type CAT-A CAT-A First Reactor Catalyst 2 Type TypeCAT-B CAT-B First Reactor Catalyst 1 Active Metal Mass wt. % 76.9 76.9Fraction (Hf/(Hf + Zr)) First Reactor Cocatalyst 1 Type Type CO-CAT-1CO-CAT-1 First Reactor Cocatalyst 2 Type Type CO-CAT-2 CO-CAT-2 FirstReactor, Molar ratio of Boron in Ratio 1.2 1.2 Cocatalyst 1 to Totalmetal in Catalysts 1 and 2 First Reactor, Molar ratio of Aluminum inRatio 10 17 Cocatalyst 2 to Total Metal in Catalysts 1 and 2 SecondReactor Feed Solvent/Ethylene g/g 5.1 5.3 Mass Flow Ratio Second ReactorFeed Comonomer/ g/g 0.24 0.00 Ethylene Mass Flow Ratio Second ReactorFeed Hydrogen/Ethylene g/g 2.82E-03 2.82E-03 Mass Flow Ratio SecondReactor Temperature ° C. 210 210 Second Reactor Pressure barg 28 28Second Reactor Ethylene Conversion % 81.4 81.9 Second Reactor CatalystType Type CAT-C CAT-C Second Reactor Cocatalyst Type Type CO-CAT-3CO-CAT-3 Second Reactor Cocatalyst to Catalyst, Al mol/mol 4.6 4.6 to Timolar ratio Melt index I₂ g/10 min 0.7 0.9 Melt index I₁₀ g/10 min 6.67.7 I₁₀/I₂ 9.4 8.6 Density g/cc 0.916 0.916

Formulas of Catalyst A and Catalyst B are shown below.

CATALYST C is a Ziegler-Natta catalyst. The heterogeneous Ziegler-Nattatype catalyst-premix was prepared substantially according to U.S. Pat.No. 4,612,300, by sequentially adding to a volume of ISOPAR-E, a slurryof anhydrous magnesium chloride in ISOPAR-E, a solution of EtAlCl₂ inheptane, and a solution of Ti(O-iPr)₄ in heptane, to yield a compositioncontaining a magnesium concentration of 0.20 M, and a ratio of Mg/Al/Tiof 40/12.5/3. An aliquot of this composition was further diluted withISOPAR-E to yield a final concentration of 500 ppm Ti in the slurry.While being fed to, and prior to entry into, the polymerization reactor,the catalyst premix was contacted with a dilute solution oftriethylaluminum (Et₃Al), in the molar Al to Ti ratio specified in Table1, to give the active catalyst. The cocatalyst compositions are listedin Table 2 below.

TABLE 2 Description Chemical Name CO-CAT-A bis(hydrogenated tallowalkyl)methylammonium tetrakis(pentafluorophenyl)borate(1-) CO-CAT-BAluminoxanes, iso-Bu Me, branched, cyclic and linear; modified methylaluminoxane CO-CAT-C Et₃Al (Triethylaluminum)

Comparative Examples 1 and 2 illustrate that drift occurs in thetrimodal polymer split for a two reactor, three catalyst system.Composition of Comparative Example 1 is tabulated in Table 3. A newbatch of CAT-A and CAT-B were used to make Comparative Example 2. Thecatalyst flow was adjusted to achieve the same reactor exit ethyleneconcentration. However, higher “First Reactor Feed Hydrogen/EthyleneMass Flow Ratio” was required for Comparative Example 2 than ComparativeExample 1. At the same target catalyst ratio, the first ethylene-basedcomponent weight fraction increased from Comparative Example 1 toComparative Example 2 as shown in FIG. 3 , indicating that catalystefficiency for CAT-A and CAT-B was impacted. The second ethylene-basedcomponent weight fraction decreased correspondingly from ComparativeExample 1 to Comparative Example 2 as shown in FIG. 3 . The peaks inFIG. 3 representing the first ethylene-based component and the secondethylene-based component varied between Comparative Example 1 andComparative Example 2. This demonstrates that controlling the respectiveweight fractions (also called the split) of the first ethylene-basedcomponent and the second ethylene-based components in a two reactor,three catalyst system is more challenging.

TABLE 3 Composition of Comparative Example 1 Density (g/cc) 1 0.886 20.908 3 0.956 M_(w(GPC)) (g/mol) 1 196,133 2 114,601 3 21,068M_(w(GPC))/M_(n(GPC)) 1 2.3 2 2.0 3 3.7 Melt Index, I₂(g/10 min) 1 0.102 0.76 3 442 Weight (Wt.) % 1 41 2 22 3 37 1 = first ethylene-basedcomponent 2 = second ethylene-based component 3 = third ethylene-basedcomponent *density of the third ethylene-based polymer componentcalculated based according to Equation 29

Without being bound to any particular theory, the weight fraction ofeach of the first, second and third components can be controlled moreeasily by a three reactor system, which can help the system achieve adesired split i.e., the desired amount of each ethylene-based componentin the multimodal ethylene-based polymer.

Example 3

Example 3 provides a simulation of a polymer produced in three CSTRs inseries, wherein the first CSTR reactor is adiabatic. The results of thesimulation are provided in Table 4, below.

TABLE 4 Example 3 Reactor Configuration Type 3-CSTR in Series Comonomertype Type 1-octene First Reactor Feed Solvent/Ethylene Mass Flow Ratiog/g 7.0 First Reactor Feed Comonomer/Ethylene Mass Flow Ratio g/g 0.56First Reactor Feed Hydrogen/Ethylene Mass Flow Ratio g/g 6.3E-05 FirstReactor Temperature ° C. 185 First Reactor Pressure barg 50 FirstReactor Ethylene Conversion % 86.0 First Reactor Catalyst 1 Type TypeCAT-A First Reactor Cocatalyst 1 Type Type CO-CAT-1 First ReactorCocatalyst 2 Type Type CO-CAT-2 First Reactor Component Polymer WeightFraction wt. % 40.0 First Reactor Component Melt Index (I₂), MI₁ g/10min 0.09 First Reactor Component Density g/cc 0.886 Second Reactor FeedSolvent/Ethylene Mass Flow Ratio g/g 3.0 Second Reactor FeedComonomer/Ethylene Mass Flow Ratio g/g 0.05 Second Reactor FeedHydrogen/Ethylene Mass Flow Ratio g/g 1.2E-05 Second Reactor Temperature° C. 165 Second Reactor Pressure barg 50 Second Reactor EthyleneConversion % 87.5 Second Reactor Catalyst 1 Type Type CAT-B SecondReactor Cocatalyst 1 Type Type CO-CAT-1 Second Reactor Cocatalyst 2 TypeType CO-CAT-2 Second Reactor Component Polymer Weight Fraction wt.% 20.5Second Reactor Component Melt Index (I₂), MI₂ g/10 min 0.80 SecondReactor Component Density g/cc 0.908 Third Reactor Feed Solvent/EthyleneMass Flow Ratio g/g 3.0 Third Reactor Feed Comonomer/Ethylene Mass FlowRatio g/g 0.05 Third Reactor Feed Hydrogen/Ethylene Mass Flow Ratio g/g3.0E-03 Third Reactor Temperature ° C. 200 Third Reactor Pressure barg50 Third Reactor Ethylene Conversion % 70.0 Third Reactor Catalyst TypeType CAT-C Third Reactor Co-Catalystl Type Type CO-CAT-3 Third ReactorComponent Polymer Weight Fraction wt. % 39.5 Third Reactor ComponentMelt Index (I₂), MI₃ g/10 min 293 Third Reactor Component Density g/cc0.953 Overall Melt Index, I₂ g/10 min 0.70 Overall Density g/cc 0.916

The Composition of the trimodal polymer can be precisely controlled bythe three reactor system. As shown in Table 4, density, melt index andweight fraction of the first, second and third ethylene-based componentscan be controlled by the “Solvent/Ethylene Mass Flow Ratio”,“Comonomer/Ethylene Mass Flow Ratio”, “Hydrogen/Ethylene Mass FlowRatio”, “Reactor Temperature”, “Reactor Pressure” and “EthyleneConversion” of each reactor, respectively. Unlike Comparative examples 1and 2 discussed above, variation in catalyst efficiency (batch-to-batch)is not of concern, as one can separately control and adjust the catalystfeed to each reactor to reach the ethylene conversion targets in eachreactor. The ethylene conversion and ethylene feed in each reactordetermine the weight fraction of the first, second, and the thirdethylene-based components.

It should be apparent to those skilled in the art that variousmodifications can be made to the described embodiments without departingfrom the spirit and scope of the claimed subject matter. Thus, it isintended that the specification cover modifications and variations ofthe described embodiments provided such modification and variations comewithin the scope of the appended claims and their equivalents.

The invention claimed is:
 1. A method of producing a trimodal polymer ina solution polymerization process comprising: introducing at least onecatalyst, ethylene monomer, at least one C₃-C₁₂ α-olefin comonomer,solvent, and optionally hydrogen to a first solution polymerizationreactor to produce an effluent comprising a first ethylene-basedcomponent, wherein the first ethylene-based component has a density (ρ₁)of 0.870 to 0.910 g/cc, and a weight-average molecular weight(M_(w(GPC),1)) of 150 to 350 kg/mol as measured according to gelpermeation chromatography (GPC); introducing the first ethylene-basedcomponent, at least one catalyst, ethylene monomer, at least one C₃-C₁₂α-olefin comonomer, solvent, and optionally hydrogen to a secondsolution polymerization reactor downstream from the first solutionpolymerization reactor to produce an effluent comprising the firstethylene-based component and a second ethylene-based component, whereinthe second ethylene-based component has a density (ρ₂) from 0.895 to0.925 g/cc, and a weight-average molecular weight (M_(w(GPC),2)) from120 to 170 kg/mol; and introducing the first ethylene-based component,the second ethylene-based component, at least one catalyst, ethylenemonomer, at least one C₃-C₁₂ α-olefin comonomer, solvent, and optionallyhydrogen to a third solution polymerization reactor downstream from thesecond solution polymerization reactor to produce an effluent comprisingthe trimodal polymer, wherein the trimodal polymer comprises the firstethylene-based component, the second ethylene-based component, and athird ethylene-based component, wherein the third ethylene-basedcomponent has a density (ρ₃) of 0.920 to 0.980 g/cc, and aweight-average molecular weight (M_(w(GPC),3)) of 18 to 60 kg/mol;wherein the first solution polymerization reactor or the third solutionpolymerization reactor is an adiabatic reactor; wherein differentcatalysts are used in the first solution polymerization reactor, thesecond solution polymerization reactor, and the third solutionpolymerization reactor; and wherein ρ₃>ρ₂>ρ₁, andM_(w(GPC),1)>M_(w(GPC),2)>M_(w(GPC),3).
 2. The method of claim 1,wherein the first ethylene-based component has a melt index (MI₁)measured according to ASTM D1238 at 190° C. and 2.16 kg load, the secondethylene-based component has a melt index (MI₂) measured according toASTM D1238 at 190° C. and 2.16 kg load, and the third ethylene-basedcomponent has a melt index (MI₃) measured according to ASTM D1238 at190° C. and 2.16 kg load, and wherein the MI₁ is less than MI₂ and isalso less than MI₃.
 3. The method of claim 2, wherein MI₁<MI₂<MI₃. 4.The method of claim 1, wherein the first solution polymerization reactoris an adiabatic reactor.
 5. The method of claim 1, wherein one or moreof the first solution polymerization reactor, the second solutionpolymerization reactor, and the third solution polymerization reactorcomprise continuous stirred tank reactors, loop reactors, orcombinations thereof.
 6. The method of claim 1, wherein the firstsolution polymerization reactor is an adiabatic continuous stirred tankreactor, and the second and third solution polymerization reactors areloop reactors.
 7. The method of claim 1, further comprising a tubularreactor downstream of the first solution polymerization reactor, thesecond solution polymerization reactor, and the third solutionpolymerization reactor, wherein the tubular reactor produces additionalpolymerization of the trimodal polymer.
 8. The method of claim 1,wherein the trimodal polymer has a density from 0.900 g/cc to 0.960g/cc, and a melt index (I₂) of from 0.1 g/10 min to 10.0 g/10 min. 9.The method of claim 1, wherein the trimodal polymer comprises 2% to 45%by weight of the first ethylene-based component; 2% to 40% by weight ofthe second ethylene-based component; and 30% to 70% by weight of thethird ethylene-based component.
 10. The method of claim 1, wherein thecatalyst in the first solution polymerization reactor, the secondsolution polymerization reactor, or both is a catalyst according toFormula (I):

wherein M is a metal chosen from titanium, zirconium, or hafnium, themetal being in a formal oxidation state of +2, +3, or +4; n is 0, 1, or2; when n is 1, X is a monodentate ligand or a bidentate ligand; when nis 2, each X is a monodentate ligand and is the same or different; themetal-ligand complex is overall charge-neutral; O is oxygen; each Z isindependently chosen from —O—, —S—, —N(R^(N))—, or —P(R^(P))—; L is(C₁-C₄₀)hydrocarbylene or (C₁-C₄₀)heterohydrocarbylene, wherein the(C₁-C₄₀)hydrocarbylene has a portion that comprises a 1-carbon atom to10-carbon atom linker backbone linking the two Z groups in Formula (I)(to which L is bonded) or the (C₁-C₄₀)heterohydrocarbylene has a portionthat comprises a 1-atom to 10-atom linker backbone linking the two Zgroups in Formula (I), wherein each of the 1 to 10 atoms of the 1-atomto 10-atom linker backbone of the (C₁-C₄₀)heterohydrocarbyleneindependently is a carbon atom or heteroatom of a heteroatom-containinggroup, wherein each heteroatom-containing group independently is O, S,S(O), S(O)₂, Si(R^(C))₂, Ge(R^(C))₂, P(R^(C)), or N(R^(C)), whereinindependently each R^(C) and each R is unsubstituted (C₁-C₁₈)hydrocarbylor —H; independently each R^(N) is unsubstituted (C₁-C₁₈)hydrocarbyl; R¹and R⁸ are independently selected from the group consisting of(C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃,—Ge(R^(C))₃, —P(R^(P))₂, —N(R^(N))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃,R^(C)S(O)—, R^(C)S(O)₂—, (R^(C))₂C═N—, R^(C)C(O)O—, R^(C)OC(O)—,R^(C)C(O)N(R^(N))—, (R^(N))₂NC(O)—, halogen, and radicals having Formula(II), Formula (III), or Formula (IV):

wherein in Formulas (II), (III), and (IV), each of R³¹⁻³⁵, R⁴¹⁻⁴⁸, orR⁵¹⁻⁵⁹ is independently chosen from (C₁-C₄₀)hydrocarbyl,(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(P))₂,—N(R^(N))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, R^(C)S(O)—, R^(C)S(O)₂—,(R^(C))₂C═N—, R^(C)C(O)O—, R^(C)OC(O)—, R^(C)C(O)N(R^(N))—,(R^(N))₂NC(O)—, halogen, or —H, provided at least one of R¹ or R⁸ is aradical having Formula (II), Formula (III), or Formula (IV); and whereineach of R²⁻⁴, R⁵⁻⁷, and R⁹⁻¹⁶ is independently selected from(C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃,—Ge(R^(C))₃, —P(R^(P))₂, —N(R^(N))₂—OR^(C), —SR^(C), —NO₂, —CN, —CF₃,R^(C)S(O)—, R^(C)S(O)₂—, (R^(C))₂C═N—, R^(C)C(O)O—, R^(C)OC(O)—,R^(C)C(O)N(R^(N))—, (R^(C))₂NC(O)—, halogen, or —H.
 11. The method ofclaim 1, wherein the catalyst in at least one of the first solutionpolymerization reactor, the second solution polymerization reactor, andthe third solution polymerization reactor is a heterogeneousZiegler-Natta catalyst.
 12. A method of producing a trimodal polymer ina solution polymerization process comprising: introducing at least onecatalyst, ethylene monomer, at least one C₃-C₁₂ α-olefin comonomer,solvent, and optionally hydrogen to a first solution polymerizationreactor to produce an effluent comprising a first ethylene-basedcomponent, wherein the first ethylene-based component has a density (ρ₁)of 0.870 to 0.910 g/cc, and a weight-average molecular weight(M_(w(GPC),1)) of 150 to 350 kg/mol as measured according to gelpermeation chromatography (GPC); introducing at least one catalyst,ethylene monomer, at least one C₃-C₁₂ α-olefin comonomer, solvent, andoptionally hydrogen to a second solution polymerization reactor toproduce an effluent comprising a second ethylene-based component,wherein the second ethylene-based component has a density (ρ₂) from0.895 to 0.925 g/cc, and a weight-average molecular weight(M_(w(GPC),2)) from 120 to 170 kg/mol; introducing at least onecatalyst, ethylene monomer, at least one C₃-C₁₂ α-olefin comonomer,solvent, and optionally hydrogen to a third solution polymerizationreactor to produce an effluent comprising a third ethylene-basedcomponent, wherein the third ethylene-based component has a density (ρ₃)of 0.920 to 0.980 g/cc, and a weight-average molecular weight(M_(w(GPC),3)) of 18 to 60 kg/mol; and mixing the first ethylene-basedcomponent, the second ethylene-based component, and the thirdethylene-based component to produce the trimodal polymer; wherein thefirst solution polymerization reactor or the third solutionpolymerization reactor is an adiabatic reactor; wherein differentcatalysts are used in the first solution polymerization reactor, thesecond solution polymerization reactor, and the third solutionpolymerization reactor; and wherein ρ₃>ρ₂>ρ₁, andM_(w(GPC),1)>M_(w(GPC),2)>M_(w(GPC),3).
 13. The method of claim 12,wherein the catalyst in at least one of the first solutionpolymerization reactor, the second solution polymerization reactor, andthe third solution polymerization reactor is a heterogeneousZiegler-Natta catalyst.
 14. The method of claim 12, wherein the firstethylene-based component is fed to the second solution polymerizationreactor, the third solution polymerization reactor, or both.
 15. Themethod of claim 12, wherein the first ethylene-based component has amelt index (MI₁) measured according to ASTM D1238 at 190° C. and 2.16 kgload, the second ethylene-based component has a melt index (MI₂)measured according to ASTM D1238 at 190° C. and 2.16 kg load, and thethird ethylene-based component has a melt index (MI₃) measured accordingto ASTM D1238 at 190° C. and 2.16 kg load, and wherein the MI₁ is lessthan MI₂ and is also less than MI₃.
 16. The method of claim 12, whereinthe trimodal polymer has a density from 0.900 g/cc to 0.960 g/cc, and amelt index (I₂) of from 0.1 g/10 min. to 10.0 g/10 min.
 17. The methodof claim 12, wherein the trimodal polymer comprises 2% to 45% by weightof the first ethylene-based component; 2% to 40% by weight of the secondethylene-based component; and 30% to 70% by weight of the thirdethylene-based component.
 18. The method of claim 12, wherein thecatalyst in the first solution polymerization reactor, the secondsolution polymerization reactor, or both is a catalyst according toFormula (I): ):

wherein M is a metal chosen from titanium, zirconium, or hafnium, themetal being in a formal oxidation state of +2, +3, or +4; n is 0, 1, or2; when n is 1, X is a monodentate ligand or a bidentate ligand; when nis 2, each X is a monodentate ligand and is the same or different; themetal-ligand complex is overall charge-neutral; O is oxygen; each Z isindependently chosen from —O—, —S—, —N(R^(N))—, or —P(R^(P))—; L is(C₁-C₄₀)hydrocarbylene or (C₁-C₄₀)heterohydrocarbylene, wherein the(C₁-C₄₀)hydrocarbylene has a portion that comprises a 1-carbon atom to10-carbon atom linker backbone linking the two Z groups in Formula (I)(to which L is bonded) or the (C₁-C₄₀)heterohydrocarbylene has a portionthat comprises a 1-atom to 10-atom linker backbone linking the two Zgroups in Formula (I), wherein each of the 1 to 10 atoms of the 1-atomto 10-atom linker backbone of the (C₁-C₄₀)heterohydrocarbyleneindependently is a carbon atom or heteroatom of a heteroatom-containinggroup, wherein each heteroatom-containing group independently is O, S,S(O), S(O)₂, Si(R^(C))₂, Ge(R^(C))₂, P(R^(C)), or N(R^(C)), whereinindependently each R^(C) and each R^(P) is unsubstituted(C₁-C₁₈)hydrocarbyl or —H; independently each R^(N) is unsubstituted(C₁-C₁₈)hydrocarbyl; R¹ and R⁸ are independently selected from the groupconsisting of (C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl,—Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(P))₂, —N(R^(N))₂, —OR^(C), —SR^(C),—NO₂, —CN, —CF₃, R^(C)S(O)—, R^(C)S(O)₂—, (R^(C))₂C═N—, R^(C)C(O)O—,R^(C)OC(O)—, R^(C)C(O)N(R^(N))—, (R^(N))₂NC(O)—, halogen, and radicalshaving Formula (II), Formula (III), or Formula (IV):

wherein in Formulas (II), (III), and (IV), each of R³¹⁻³⁵, R⁴¹⁻⁴⁸, orR⁵¹⁻⁵⁹ is independently chosen from (C₁-C₄₀)hydrocarbyl,(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(P))₂,—N(R^(N))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, R^(C)S(O)—, R^(C)S(O)₂—,(R^(C))₂C═N—, R^(C)C(O)O—, R^(C)OC(O)—, R^(C)C(O)N(R^(N))—,(R^(N))₂NC(O)—, halogen, or —H, provided at least one of R¹ or R⁸ is aradical having Formula (II), Formula (III), or Formula (IV); and whereineach of R²⁻⁴, R⁵⁻⁷, and R⁹⁻¹⁶ is independently selected from(C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃,—Ge(R^(C))₃, —P(R^(P))₂, —N(R^(N))₂—OR^(C), —SR^(C), —NO₂, —CN, —CF₃,R^(C)S(O)—, R^(C)S(O)₂—, (R^(C))₂C═N, R^(C)C(O)O—, R^(C)OC(O)—,R^(C)C(O)N(R^(N))—, (R^(C))₂NC(O)—, halogen, or —H.